Coordination metal compound, material for organic electroluminescence device, material for luminescent coating formation and organic electroluminescence device

ABSTRACT

A coordination metal compound comprising cordinating at least one ligand having a Spiro bond to at least a metal atom; a material for an organic electroluminescence (EL) device, and an organic EL device comprising at least one organic thin film layer sandwiched between a pair of electrodes consisting of an anode and a cathode, wherein at least one organic thin film layer thereof comprises the coordination metal compound or the material for an organic EL device, and a material for luminescence coating formation comprising an organic solvent solution containing the coordination metal compound or the material for the organic EL device is provided. Further, the organic EL device employing either the material for luminescence coating formation or the material for the organic EL device, which exhibits an enhanced efficiency of light emission and is superior in heat resistance, the coordination metal compound having excellent solubility for an organic solvent which realizes the aforementioned, the material for the organic EL device and the material for luminescence coating formation are provided.

TECHNICAL FIELD

The present invention relates to a coordination metal compound, amaterial for an organic electroluminescence device, a material forluminescent coating formation and an organic electroluminescence device.The present invention relates, in particular, to an organicelectroluminescence device having a great efficiency of light emissionand significant storage stability at elevated temperature, acoordination metal compound which realizes the aforementioned, hasexcellent solubility in an organic solvent and can be applied to anorganic electroluminescence device by using a simple wet film formingprocess as well as a vacuum deposition process, a material for anorganic electroluminescence device and a material for luminescentcoating formation.

BACKGROUND ART

An organic electroluminescence (“electroluminescence” will beoccasionally referred to as “EL”, hereinafter) device is a spontaneouslight emitting device which utilizes the principle that a fluorescentsubstance emits light by energy of recombination of holes injected froman anode and electrons injected from a cathode when an electric field isapplied. Since an organic EL device of the laminate type driven under alow electric voltage was reported by C. W. Tang et al. of Eastman KodakCompany (C. W. Tang and S. A. Vanslyke, Applied Physics Letters, Volume51, Pages 913, 1987), many studies have been conducted on organic ELdevices using organic materials as the constituting materials. Tang etal. used a laminate structure using tris(8-hydroxyquinolinol aluminum)for the light emitting layer and a triphenyldiamine derivative for thehole transporting layer. Advantages of the laminate structure are thatthe efficiency of hole injection into the light emitting layer can beincreased, that the efficiency of forming excited particles which areformed by blocking and recombining electrons injected from the cathodecan be increased, and that excited particles formed among the lightemitting layer can be enclosed. As the structure of the organic ELdevice, a two-layered structure having a hole transporting (injecting)layer and an electron transporting and light emitting layer and athree-layered structure having a hole transporting (injecting) layer, alight emitting layer and an electron transporting (injecting) layer arewell known. To increase the efficiency of recombination of injectedholes and electrons in the devices of the laminate type, the structureof the device and the process for forming the device have been studied.

As the light emitting material of the organic EL device, chelatecomplexes such as tris(8-quinolinolato)aluminum, coumarine derivatives,tetraphenylbutadiene derivatives, bisstyrylarylene derivatives andoxadiazole derivatives are known. It is reported that light in thevisible region ranging from blue light to red light can be obtained byusing these light emitting materials, and development of a deviceexhibiting color images is expected (refer to, for example, JapanesePatent Application Laid-Open Nos. Heisei 8(1996)-239655, Heisei7(1995)-138561 and Heisei 3(1991)-200289).

In addition, it has been recently proposed that an organicphosphorescent material is applied to a light emitting layer besides alight emitting material (refer to, for example, D. F. O'Brien and M. A.Baldo et al “Improved energy transferring electro phosphorescentdevices” Applied Physics letters Vol. 74 No. 3, pp 442-444, Jan. 18,1999: M. A. Baldo et al “Very high-efficiency green organiclight-emitting devices based on electro phosphorescence” Applied Physicsletters Vol. 75 No. 1, pp 4-6, Jul. 5, 1999).

A great efficiency of light emission has been achieved by utilizing asinglet state and a triplet state of the organic phosphorescentmaterials in a light emitting layer of an organic EL device. Since ithas been considered that singlet exciton and triplet exciton are formedat a ratio between the two of 1 to 3 due to difference of spinmultiplicity thereof on recombination of electrons and holes in anorganic EL device, it should be understood that three to four timeshigher efficiency of light emission can be achieved by utilizing anphosphorescent light emitting material than by utilizing only afluorescent light emitting material.

In the above organic EL devices, in order for triplet excited state orexcitons in triplet state not to diminish, a construction comprised bylaminating sequentially an anode, a hole transporting layer, an organiclight emitting layer, an electron transporting layer (a hole blockinglayer), an electron injecting layer, a cathode and so forth has beenemployed and a host compound, and a phosphorescent compound have beenemployed as an organic light emitting layer (refer to, for examples,U.S. Pat. No. 6,097,147 and International PCT Publication NO. WO01/41512). In the patent literatures, N,N′-dicarbazole-biphenyl has beenemployed as a host compound. However, it is easily crystallized becauseof its glass transition temperature of 110° C. or less and also becauseof its excessively good symmetric property. In addition, there is aproblem of resulting in short circuit or pixel deficiency thereof on aheat resistant test of a device.

Further, crystal growth occurred at a place where there are foreignmaterials or a raised portion of a electrode, therefore moredeficiencies after the heat resistant test have been found than thosebefore the test. In addition, a carbazole derivative having tri-symmetryhas been employed as a host material. However, due to its good symmetricproperty, crystal growth was occurred at a place where there are foreignmaterials or a raised portion of a electrode on vapor deposition,therefore, it has not been freed from causing more deficiencies thanthose existed in the initial stage before the heat resistant test.

An iridium complex has been generally employed as a phosphorescentcompound and a light emitting layer has been formed from a mixturecomprised a host compound containing a certain part (a few % by mass orless) of an iridium complex. Generally, the higher content of aphosphorescent compound to a host compound tends to the higherluminescence intensity, however, in the case of a few % to several dozen% thereof, the luminescence intensity decreases and also luminance ofemitted light of the device decreases due to imbalance between them. Ithas been known as concentration quenching or concentration deactivationas described in Japanese Unexamined Patent Application Laid-Open No.Heisei 05 (1993)-078655; Japanese Unexamined Patent ApplicationLaid-Open No. Heisei 05 (1993)-320633. The above has been considered tobe related to non-irradiative transition caused by multimerizationreaction between materials for luminescence center or with a neighboringmaterial thereof. With this view, it has been not possible to use plentyof a phosphorescent compound for promoting the efficiency thereof;therefore, optimization of the concentration has been required.

Recently, the research progress of improvement on phosphorescentcompounds has resulted in providing a phosphorescent compound to beemployed for a wet film forming process which has been a simple and easyway of fabricating a device (refer to, Shao-An Chen et al,“High-Efficiency Red-Light Emission from Polyfuluorenes Grafted withCyclometalated Iridium Complexes and Charge Transport Moiety”, J. Am.Chem. Soc., Vol. 125, pp 636-637, 2003; and U.S. Laid-Open PatentPublication No. 2003-0091862A1). However, the current materials show lowluminance of light emission, and stability of devices employed thematerials under elevated temperature is poor; therefore they are oflittle practical use.

DISCLOSURE OF THE INVENTION

The present invention has been made to overcome the above problems andhas an object of providing an organic EL device having a great luminanceof emitted light and great storage stability under high temperature. Thepresent invention also has an objective of providing a coordinationmetal compound having favorable solubility to organic solvents, amaterial for the organic EL device and a material for luminescentcoating formation for realizing the organic EL device.

As a result of intensive researches and studies to achieve the aboveobjectives by the present inventors, it was found that employing acoordination metal compound containing a spiro bond as an light emittingmaterial enables to provide an organic electroluminescence device havinga great luminance of emitted light and great storage stability underelevated temperature because of the controlled association between themolecules. Such being the case, the present invention has beenaccomplished on the basis of the foregoing findings and information. Inaddition, the coordination metal complexes show excellent solubility foran organic solvent so that it is possible to apply them to a wet filmforming process such as a spin coating process.

Namely, the present invention provides a coordination metal complexcomprising a metal atom coordinated with at least a ligand having aspiro bond. Here, “coordination” means to form a coordination bondbetween a lone pair of a hetero atom of a ligand and a metal atom whileforming a carbon atom-a metal atom bond between a ligand and a metalatom.

Further, the present invention provides a material for an organic ELdevice, which comprises at least one compound selected from thecompounds represented by the general formula (1′):

wherein X, Y¹ and Y² each independently represents a single bond,—CR′R″—, —SiR′R″—, —CO— or —NR′—; Q represents a carbon atom, a siliconatom or a germanium atom; Z represents a divalent group comprising aheavy metal complex; R′ and R″ each independently represents a hydrogenatom, a substituted or unsubstituted aromatic group having 6 to 50 ringcarbon atoms, a substituted or unsubstituted aromatic heterocyclic grouphaving 5 to 50 ring atoms, or a substituted or unsubstituted alkyl grouphaving 1 to 50 carbon atoms; R¹ to R⁸ each independently represents ahydrogen atom or a group selected from among a substituted orunsubstituted alkyl group having 1 to 50 carbon atoms, a substituted orunsubstituted alkenyl group having 1 to 50 carbon atoms, a substitutedor unsubstituted alkynyl group having 1 to 50 carbon atoms, asubstituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, asubstituted or unsubstituted alkylthio group having 1 to 50 carbonatoms, a substituted or unsubstituted amino group having 1 to 50 carbonatoms, a substituted or unsubstituted alkylamino group having 1 to 50carbon atoms, a substituted or unsubstituted dialkylamino group having 1to 50 carbon atoms or a substituted or unsubstituted heterocyclic grouphaving 1 to 50 carbon atoms, and an aryl group having 6 to 50 carbonatoms, an aryloxy group having 6 to 50 carbon atoms, an arylthio grouphaving 6 to 50 carbon atoms, an arylamono group having 6 to 50 carbonatoms, a diarylamino group having 6 to 50 carbon atoms or analkylarylamino group having 6 to 50 carbon atoms; in addition, twoneighboring groups among R¹ to R⁸ may bond each other to form a ringstructure; a material for an organic EL device represents by the generalformula (4′):(E¹)—(C¹)_(p1)-(C²)_(p2)-(Phos)-(C³)_(p3)—(C⁴)_(p4)-(E²)  (4′)wherein (Phos) represents a divalent group formed by removing two fromamong R¹ to R⁸; E¹ to E² each independently represents a hydrogen atom,or a group selected from among a substituted or unsubstituted aromaticgroup having 6 to 50 ring carbon atoms, a substituted or unsubstitutedaromatic heterocyclic group having 5 to 50 ring atom, a substituted orunsubstituted alkyl group having 1 to 50 carbon atoms, a substituted orunsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted orunsubstituted aralkyl group having 7 to 50 carbon atoms, a substitutedor unsubstituted aryloxy group having 5 to 50 ring atoms, a substitutedor unsubstituted arylthio group having 5 to 50 ring atoms, a substitutedor unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, acarboxyl group, a halogen atom, a cyano group and a hydroxyl group; C¹to C⁴ each independently represents a group selected from a substitutedor unsubstituted alkylene group having 1 to 50 carbon atoms and asubstituted or unsubstituted divalent aryl group having 6 to 50 carbonatoms; p1 to p4 each independently represents an integer of from 0 to20;a material for an organic EL device which comprises a polymer obtainedby polymerization or co-polymerization of a compound represented by thegeneral formula (1′), of which at least one of among R¹ to R⁸ representsa polymerizable group or an aromatic group having 6 to 50 ring carbonatoms posessing a polymerizable group, anda material for an organic EL device which comprises a polymer or acopolymer comprising a unit structure of a divalent group formed byremoving two selected from among R¹ to R⁸ in the general formula (1′).

Further, the present invention provides an organic EL device comprisingat least one organic thin film layers including a light emitting layersandwiched between a pair of electrodes consisting of an anode and acathode, wherein at least one of the organic thin film layers comprisesthe coordination metal compound or the material for the organic ELdevice.

Moreover, the present invention provides a material for luminescentcoating formation comprising an organic solvent solution containing thecoordination metal compound or the material for the organic EL device,and also an organic EL device fabricated by using the material forluminescent coating formation or the material for the organic EL device.

THE PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION

Firstly, a coordination metal compound of the present invention will beexplained below.

The coordination metal compound means a coordination metal compoundformed by coordinating at least one ligand having a spiro bond and anyone of the compounds represented by the general formula (1) ispreferred.(L₁)x-M-(P-M)y-(L₂)z  (1)

In the general formula (1), L₁ represents a ligand coordinating to ametal atom M and having a spiro bond.

Further, it is preferable that L₁ in the general formula (1) is a ligandrepresented by a following general formula (2):A-(C)p-(B)q—(C)p-D-  (2)

To begin with, A in the general formula (2) will be explained below:

In the general formula (2), A represents a group expressed by followinggeneral formulae (3) to (12):

In the general formulae (3) to (12), R independently represents asubstituted or unsubstituted aromatic group having 6 to 50 ring carbonatoms, a substituted or unsubstituted aromatic heterocyclic group having5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1to 50 carbon atoms, a substituted or unsubstituted aralkyl group having7 to 50 carbon atoms, a substituted or unsubstituted aryloxy grouphaving 5 to 50 ring atoms, a substituted or unsubstituted arylthio grouphaving 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonylgroup having 1 to 50 carbon atoms, a carboxyl group, a halogen atom, acyano group, a nitro group or a hydroxyl group; R may bond each other toform a ring structure.

In the general formulae (3) to (12), a and b each independentlyrepresents an integer of from 0 to 4; c, d, e and f each independentlyrepresents an integer of from 2 to 4.

Examples of the substituted or unsubstituted aromatic group having 6 to50 ring carbon atoms represented by R include phenyl group, 1-naphthylgroup, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthrylgroup, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group,4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group,2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenylgroup, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group,4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group,p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group,m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group,p-t-butylphenyl group, p-(2-phenylpropyl)phenyl group,3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthrylgroup, 4′-methylbiphenyl-yl group, 4″-t-butyl-p-terphenyl-4-yl group andthe like.

Examples of the substituted or unsubstituted aromatic heterocyclic grouphaving 5 to 50 ring atoms represented by R include 1-pyrrolyl group,2-pyrrolyl group, 3-pyrrolyl group, pyradinyl group, pyrimidyl group,pyridazyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinylgroup, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolylgroup, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolylgroup, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group,5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furylgroup, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group,4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group,7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group,4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranylgroup, 7-isobenzofuranyl group, quinolyl group, 3-quinolyl group,4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group,8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group,4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group,7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxanyl group,5-quinoxanyl group, 6-quinoxanyl group, 1-phenanthridinyl group,2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinylgroup, 6-phenanthridinyl group, 7-phenanthridinyl group,8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinylgroup, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group,4-acridinyl group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group,1,7-phenanthrolin-3-yl group, 1,7-phenanthrolin-4-yl group,1,7-phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group,1,7-phenanthrolin-8-yl group, 1,7-phenanthrolin-9-yl group,1,7-phenanthrolin-10-yl group, 1,8-phenanthrolin-2-yl group,1,8-phenanthrolin-3-yl group, 1,8-phenanthrolin-4-yl group,1,8-phenanthrolin-5-yl group, 1,8-phenanthrolin-6-yl group,1,8-phenanthrolin-7-yl group, 1,8-phenanthrolin-9-yl group,1,8-phenanthrolin-10-yl group, 1,9-phenanthrolin-2-yl group,1,9-phenanthrolin-3-yl group, 1,9-phenanthrolin-4-yl group,1,9-phenanthrolin-5-yl group, 1,9-phenanthrolin-6-yl group,1,9-phenanthrolin-7-yl group, 1,9-phenanthrolin-8-yl group,1,9-phenanthrolin-10-yl group, 1,10-phenanthrolin-2-yl group,1,10-phenanthrolin-3-yl group, 1,10-phenanthrolin-4-yl group,1,10-phenanthrolin-5-yl group, 2,9-phenanthrolin-1-yl group,2,9-phenanthrolin-3-yl group, 2,9-phenanthrolin-4-yl group,2,9-phenanthrolin-5-yl group, 2,9-phenanthrolin-6-yl group,2,9-phenanthrolin-7-yl group, 2,9-phenanthrolin-8-yl group,2,9-phenanthrolin-10-yl group, 2,8-phenanthrolin-1-yl group,2,8-phenanthrolin-3-yl group, 2,8-phenanthrolin-4-yl group,2,8-phenanthrolin-5-yl group, 2,8-phenanthrolin-6-yl group,2,8-phenanthrolin-7-yl group, 2,8-phenanthrolin-9-yl group,2,8-phenanthrolin-10-yl group, 2,7-phenanthrolin-1-yl group,2,7-phenanthrolin-3-yl group, 2,7-phenanthrolin-4-yl group,2,7-phenanthrolin-5-yl group, 2,7-phenanthrolin-6-yl group,2,7-phenanthrolin-8-yl group, 2,7-phenanthrolin-9-yl group,2,7-phenanthrolin-10-yl group, 1-phenazinyl group, 2-phenazinyl group,1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group,4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group,2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group,10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolylgroup, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group,2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group,2-methylpyrrol-3-yl group, 2-methylpyrrol-4-yl group,2-methyl-pyrrol-5-yl group, 3-methylpyrrol-1-yl group,3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group,3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group,3-(2-phenylpropyl)pyrrol-1-yl group, 2-methyl-1-indolyl group,4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolylgroup, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group,2-t-butyl-3-indolyl group and 4-t-butyl-3-indolyl group and the like.

Examples of the substituted or unsubstituted alkyl group having 1 to 50carbon atoms represented by R include methyl group, ethyl group, propylgroup, isopropyl group, n-butyl group, s-butyl group, isobutyl group,t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octylgroup, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group,2-hydroxyisobutyl group, 1,2-dihydroxyethyl group,1,3-dihydroxy-isopropyl group, 2,3-dihydroxy-t-butyl group,1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group,2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group,1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group,1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group,2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group,1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group,1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group,2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group,1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropylgroup, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group,2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropylgroup, 2,3-diamino-t-butyl group, 1,2,3-triamino-propyl group,cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group,2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropylgroup, 2,3-dicyano-t-butyl group, 1,2,3-tricyano-propyl group,nitromethyl group, 1-nitroethyl group, 2-nitroethyl group,2-nitroisobutyl group, 1,2-dinitroethyl group, 1,3-dinitroisopropylgroup, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group,cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexylgroup, 4-methylcyclohexyl group, 1-adamanthyl group, 2-adamanthyl group,1-norbornyl group, 2-norbornyl group and the like.

The substituted or unsubstituted alkoxyl group having 1 to 50 carbonatoms represented by R is a group expressed by —OY. Examples of thegroup represented by Y include methyl group, ethyl group, propyl group,isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butylgroup, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group,hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group,2-hydroxyisobutyl group, 1,2-dihydroxyethyl group,1,3-dihydroxy-isopropyl group, 2,3-dihydroxy-t-butyl group,1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group,2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group,1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group,1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group,2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group,1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group,1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group,2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group,1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropylgroup, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group,2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropylgroup, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group,cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group,2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropylgroup, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group,nitromethyl group, 1-nitroethyl group, 2-nitroethyl group,2-nitroisobutyl group, 1,2-dinitro-ethyl group, 1,3-dinitroisopropylgroup, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group and thelike.

Examples of the substituted or unsubstituted aralkyl group having 7 to50 carbon atoms represented by R include benzyl group, 1-phenylethylgroup, 2-phenylethyl group, 1-phenyl-isopropyl group, 2-phenylisopropylgroup, phenyl-t-butyl group, α-naphthylmethyl group, 1-α-naphthylethylgroup, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group,2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethylgroup, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group,2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2-(1-pyrrolyl)ethylgroup, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group,p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group,p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group,p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group,p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group,p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group,p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group,p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group,1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group andthe like.

The substituted or unsubstituted aryloxyl group having 5 to 50 ringatoms represented by R is a group expressed by —OY′. Examples of thegroup represented by Y′ include phenyl group, 1-naphthyl group,2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group,1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group,4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group,2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenylgroup, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group,4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group,p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group,m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group,p-t-butylphenyl group, p-(2-phenylpropyl)phenyl group,3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthrylgroup, 4′-methylbiphenylyl group, 4″-t-butyl-p-terphenyl-4-yl group,2-pyrrolyl group, 3-pyrrolyl group, pyradinyl group, 2-pyridinyl group,3-pyridinyl group, 4-pyridinyl group, 2-indolyl group, 3-indolyl group,4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group,1-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolylgroup, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furylgroup, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group,5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group,1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranylgroup, 5-isobenzofuranyl group, 6-isobenzofuranyl group,7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolylgroup, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolylgroup, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group,5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group,8-isoquinolyl group, 2-quinoxanyl group, 5-quinoxanyl group,6-quinoxanyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolylgroup, 4-carbazolyl group, 1-phenanthridinyl group, 2-phenanthridinylgroup, 3-phenanthridinyl group, 4-phenanthridinyl group,6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinylgroup, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinylgroup, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group,9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-ylgroup, 1,7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group,1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group,1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group,1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group,1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group,1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group,1,8-phenanthrolin-9-yl group, 1,8-phenanthrolin-10-yl group,1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group,1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group,1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group,1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group,1,10-phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group,1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group,2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group,2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group,2,9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group,2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group,2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group,2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group,2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group,2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group,2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3-yl group,2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group,2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group,2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group,1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group,2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group,1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group,4-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolylgroup; 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group,2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group,2-methylpyrrol-3-yl group, 2-methylpyrrol-4-yl group,2-methyl-pyrrol-5-yl group, 3-methylpyrrol-1-yl group,3-methyl-pyrrol-2-yl group, 3-methylpyrrol-4-yl group,3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group,3-(2-phenylpropyl)pyrrol-1-yl group, 2-methyl-1-indolyl group,4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolylgroup, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group,2-t-butyl-3-indolyl group, 4-t-butyl-3-indolyl group and the like.

The substituted or unsubstituted arylthio group having 5 to 50 ringatoms represented by R is a group expressed by —SY′ and examples of Y′include the same as aforementioned.

The substituted or unsubstituted alkoxycarbonyl group having 1 to 50ring carbon atoms represented by R is a group expressed by —COOY andexamples of Y include the same as aforementioned.

In the general formula (3) to (12), V represents a single bond,—CR₀R₀′—, —SiR₀R₀′—, —O—, —CO— or —NR₀ wherein R₀ and R₀′ eachindependently represents a hydrogen atom, a substituted or unsubstitutedaromatic group having 6 to 50 ring carbon atoms, a substituted orunsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, ora substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.Specific examples of the above aromatic hydrocarbon group, the abovearomatic heterocyclic group and the above alkyl group include the sameas those of aforementioned about R.

In the general formula (3) to (12), E represents a ring structure shownby a circle enclosing the symbol E, and a substituted or unsubstitutedcycloalkane moiety having 3 to 6 ring carbon atoms, whose carbon atommay be substituted by a nitrogen atom, a substituted or unsubstitutedaromatic hydrocarbon moiety having 4 to 6 ring carbon atoms, or asubstituted or unsubstituted aromatic heterocyclic moiety having 4 to 6ring atoms.

Specific examples of the aromatic hydrocarbon moiety and the aromaticheterocyclic moiety include a divalent moiety having suitable carbonnumbers selected from among the groups of aforementioned about R. Inaddition, examples of the cycloalkane moiety having 3 to 6 ring carbonatoms, whose carbon atom may be substituted by a nitrogen atom include adivalent moiety such as cyclopropane, cyclobutane, cyclopentane,cyclohexane, cycloheptane, pyrrolidine, piperidine, piperazine and soforth.

In the general formula (3) to (12), Q represents an atomic group forminga ring structure and examples include an alkylene group such as anethylene group, a propylene group, n-butylene group, n-pentylene groupand n-hexylene, a group forming a heterocyclic ring by substituting anitrogen atom or an oxygen atom for at least one carbon atom of thesealkylene groups and so forth; these groups each may has a substituent,and also a saturated or an unsaturated ring may be formed by bonding thegroups each other.

In the general formulae (3) to (12), Z represents —CR₀R₀′—, —SiR₀R₀—, or—GeR₀R₀—; Ge means a germanium atom, and R₀ and R₀′ represent the sameas aforementioned.

It is preferable that the general formula (3) is any one group expressedby following general formulae (22) to (25).

In the general formulae (22) to (25), R, a and b each independentlyrepresents the same as aforementioned, and R₁ to R₈ each independentlyrepresents the same as aforementioned about R.

Further, examples of the group expressed by the general formulae (22) to(25) are shown as follows, but not limited thereto.

It is preferable that the general formula (4) is any one group expressedby following general formulae (26) to (29).

In the general formulae (26) to (29), R, a and b each independentlyrepresents the same as aforementioned, and R₁ to R₈ each independentlyrepresents the same as aforementioned about R.

Further, examples of the group expressed by the general formulae (26) to(29) are shown as follows, but not limited thereto.

Examples of the group expressed by the general formula (5) are shown asfollows, but not limited thereto.

Examples of the group expressed by the general formula (6) are shown asfollows, but not limited thereto.

It is preferable that the general formula (7) specifically coincideswith a following general formula (30).

In the general formula (30), R, V, a and b each independently representsthe same as aforementioned. A₁ to A₄ each independently represents—CR′R″—, —SiR′R″—, —O—, —NR′—, —CO—; wherein, R′ and R″ each representsthe same as R aforementioned, and R′ and R″ are the same with ordifferent from each other. In addition, at least two neighboring groupsamong A₁ to A₄ are expressed by —CR′R″—; and the neighboring R′s, theneighboring R″s or both R′ and R″ may saturatedly or unsaturatedly bondresultantly forming a ring structure having 4 to 50 carbon atoms; wrepresents an integer of from 1 to 10.

In addition, examples of the group expressed by the general formula (30)are shown as follows, but not limited thereto.

It is preferable that the general formula (8) specifically coincideswith a following general formula (31).

In the general formula (31), R, V, a, b, A₁ to A₄ and w eachindependently represents the same as aforementioned.

In addition, examples of the group expressed by the general formula (31)are shown as follows, but not limited thereto.

It is preferable that the general formula (9) specifically coincideswith any one group expressed by following general formulae (32) to (35).

In the general formulae (32) to (35), R, a, b and c each independentlyrepresents the same as aforementioned, and R₁ to R₈ each independentlyrepresents the same as aforementioned about R.

In addition, examples for a group of the general formulae (32) to (35)are shown as follows, but not limited thereto.

It is preferable that the general formula (10) specifically coincideswith any one group expressed by following general formulae (36) to (39).

In the general formulae (36) to (39), R, a, b and c each independentlyrepresents the same as aforementioned, and R₁ to R₈ each independentlyrepresents the same as aforementioned about R.

In addition, examples for a group of the general formulae (36) to (39)are shown as follows, but not limited thereto.

It is preferable that the general formula (11) specifically coincideswith a following general formula (40):

In the general formula (40), R, V, a, b, A₁ to A₄, w and e eachindependently represents the same as aforementioned.

In addition, examples for a group of the general formula (40) are shownas follows, but not limited thereto.

It is preferable that the general formula (12) specifically coincideswith a following general formula (41):

In the general formula (41), R, V, a, b, A₁ to A₄, w and f eachindependently represents the same as aforementioned.

In addition, examples for a group of the general formula (41) are shownas follows, but not limited thereto.

Next, B in the general formula (2) will be explained below.

In the general formula (2), B represents a group shown by the generalformulae (13) to (15), and may be composed of each group singly or incombination thereof, q represents an integer of from 0 to 20, preferably0 to 10.

In the general formulae (13) to (15), R, V, E, Z, Q, a and b eachindependently represents the same as aforementioned.

It is preferable that the general formula (13) and the general formula(14) each specifically coincides with following general formula (42) andthe general formula (43) respectively.

In the general formulae (42) and (43), R, V, a, b, A₁ to A₄ and w eachindependently represents the same as aforementioned.

In addition, examples for a group of the general formula (42) are shownas follows, but not limited thereto.

In addition, examples for a group of the general formula (43) are shownas follows, but not limited thereto.

It is preferable that the general formula (15) specifically coincideswith a following general formula (44):

In the general formulae (44), R represents the same as aforementioned.

Next, C in the general formula (2) will be explained below.

In the general formula (2), C represents a substituted or unsubstitutedalkylene group having 1 to 50 carbon atoms, or a substituted orunsubstituted aromatic hydrocarbon group having 6 to 50 ring carbonatoms and plural C, if any, may be the same with or different from eachother; p represents an integer of from 0 to 20, preferably 0 to 10.

Examples of the substituted or unsubstituted alkylene group having 1 to50 carbon atoms represented by C include methylene group, ethylenegroup, propylene group, isopropylene group, n-butylene group, s-butylenegroup, isobutylene group, dimetylmethylene group, n-pentylene group,n-hexylene group, n-heptylene group, n-octylene group, chloromethylenegroup, 1-chloroethylene group, 2-chloroethylene group,2-chloroisobutylene group, 1,2-dichloroethylene group,1,3-dichloroisopropylene group, 1,2,3-trichloropropylene group,bromomethylene group, 1-bromoethylene group, 2-bromoethylene group,2-bromoisobutylene group, 1,2-dibromoethylene group,1,3-dibromoisopropylene group, 1,2,3-tribromopropylene group,iodomethylene group, 1-iodoethylene group, 2-iodoethylene group,2-iodoisobutylene group, 1,2-diiodoethylene group,1,3-diiodoisopropylene group, 1,2,3-triiodopropylene group,cyclopropylene group, cyclobutylene group, cyclopentylene group,cyclohexylene group, 4-methylenecyclohexylene group, adamantane-1,1-diylgroup, adamantane-1,3-diyl group and so forth.

Examples of the substituted or unsubstituted aromatic hydrocarbon grouphaving ring carbon atoms of 6 to 50 represented by C include thefollowing:

Next, D in the general formula (2) will be explained below.

In the general formula (2), it is preferable that D coordinating to ametal atom represents a group removing a hydrogen atom from the moleculeexpressed by the general formula (20).

wherein Q₁ and Q₂ each independently represents a substituted orunsubstituted aromatic hydrocarbon group having 6 to 50 ring carbonatoms, a substituted or unsubstituted aromatic heterocyclic group having5 to 50 ring atoms of or a derivative thereof, at least one of Q₁ and Q₂represents a benzene ring or a derivative thereof, any one of Q₁ and Q₂forms a carbon atom a metal atom bond with the aforementioned metal atomM and the other one forms a coordination bond therewith.

An aromatic hydrocarbon group and an aromatic heterocyclic group of Q₁and Q₂ include the same as those of the aforementioned R. Z₃ representsa single bond, —CR₀R₀′—, —SiR₀R₀′—, —O—, —CO— or NR₀; R₀ and R₀′represent the same as aforementioned.

In addition, examples of a group represented by the general formula (20)are shown as follows, but not limited thereto.

It is preferable that D in the general formula (2) represents asubstituted or unsubstituted phenylpyridiyl group.

In addition, A and/or B in the general formula (2) contains at least onestructure having a spiro skeleton structure.

Further, regarding with the coordination metal compound of the presentinvention, it is preferable that A in the general formula (2) is any oneselected from among the foregoing general formulae (5) to (6) and (22)to (41) and that B in the general formula (2) is any one selected fromamong the foregoing general formulae (42) to (44).

Moreover, it is preferable that L₁ in the general formula (1) may alsobe a ligand represented by a following general formula (16):

In the general formula (16), A represents a group expressed by any oneof the general formulae (3) to (12), and plural A, if any, may be thesame with or different from each other. R, V, E, Q, Z and a to f in thegeneral formulae (3) to (12) each independently represents the same asaforementioned.

C in the general formula (16) may be the same as aforementioned andplural C, if any, may be the same with or different from each other. s,t and u each independently represents an integer of 0 to 20, preferably0 to 10.

B in the general formula (16) represents a tervalent group representedby any one of the general formulae (17) to (19) below, which may bealone or in combination of two or more kind thereof.

R, V, Z, Q, a and b in the general formulae (17) to (19) eachindependently represents the same as aforementioned.

It is preferable that a group of the general formula (17) is expressedby the general formula (45) below.

In the general formula (45), R, a and b each independently representsthe same as aforementioned.

It is preferable that the above general formula (18) specificallycoincides with a following general formula (46):

R, V, a, b, A₁ to A₄ and w in the general formula (46) eachindependently represents the same as aforementioned.

In addition, examples for a group of the general formula (45) and thegeneral formula (46) are shown as follows, but not limited thereto.

In the general formula (16), it is preferable that D coordinating to ametal atom represents a group removing a hydrogen atom from the moleculeexpressed by the general formula (20).

In the general formula (16), D is preferably a substituted orunsubstituted phenylpyridyl group.

Further, in the general formula (16), A and/or B contains at least onestructure having a spiro skeleton structure.

In addition, it is preferable that A represents a group selected fromthe general formulae (22) to (41) and that B represents the foregoinggeneral formulae (45) to (46).

In the general formula (1), x represents an integer of from 1 to thevalence of a metal atom M, y represents an integer of from 0 to 4 and zrepresents an integer of from 0 to 4.

M in the general formula (1) is any one of a metal atom of iridium (Ir),platinum (Pt), osmium (Os), rhodium (Rh), rhenium (Re), palladium (Pd),ruthenium (Ru), tungsten (W), gold (Au) or silver (Ag), and Ir ispreferred. Further, plural M is the same with or different from eachother when y is 1 or greater.

P in the general formula (1) represents a ligand combining with a metalatom M when y is 1 or greater, and examples thereof are as follows, butnot limited thereto.

L₂ in the general formula (1) represents a ligand coordinating to ametal atom M and may be the same as aforementioned about L₁, examplesinclude a halogen atom such as F, Cl, Br and I, an alkyl group and anaryl group having a hetero atom, an aromatic heterocyclic group and soforth; while at least one kind selected from among a halogen atom, anacetylaceton derivative, a 8-quinolinol derivative and a phenylpyridinederivative is preferable for L₂. Examples of L₂ are shown as follows,but not limited thereto.

Specific examples of a coordination metal compound represented by thegeneral formula (1) of the present invention are shown as follows, butnot limited thereto;

Next, a material for an organic EL device of the present invention willbe explained below.

A material for an organic EL device of the present invention comprisesat least one compound having a structure represented by a followinggeneral formula (1′):

In the general formula (1′), X, Y¹ and Y² each independently representsa single bond, —CR′R″—, —SiR′R″—, —CO— or NR′—, and Q represents acarbon atom, a silicon atom or a germanium atom. Z represents a divalentgroup comprising a heavy metal complex. R′ and R″ each independentlyrepresents a hydrogen atom, a substituted or unsubstituted aromaticgroup having 6 to 50 ring carbon atoms, a substituted or unsubstitutedaromatic heterocyclic group having 5 to 50 ring atoms, or a substitutedor unsubstituted alkyl group having 1 to 50 carbon atoms;

R¹ to R⁸ each independently represents a hydrogen atom or a groupselected from among a substituted or unsubstituted alkyl group having 1to 50 carbon atoms, a substituted or unsubstituted alkenyl group having1 to 50 carbon atoms, a substituted or unsubstituted alkynyl grouphaving 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy grouphaving 1 to 50 carbon atoms, a substituted or unsubstituted alkylthiogroup having 1 to 50 carbon atoms, a substituted or unsubstituted aminogroup, having 1 to 50 carbon atoms a substituted or unsubstitutedalkylamino group having 1 to 50 carbon atoms, a substituted orunsubstituted dialkylamino group having 1 to 50 carbon atoms or asubstituted or unsubstituted heterocyclic group having 1 to 50 ringcarbon atoms, and an aryl group having 6 to 50 ring carbon atoms, anaryloxy group having 6 to 50 ring carbon atoms, an arylthio group having6 to 50 ring carbon atoms, an arylamono group having 6 to 50 ring carbonatoms, a diarylamino group having 6 to 50 ring carbon atoms or analkylarylamino group having 6 to 50 ring carbon atoms. In addition, twoneighboring groups among R¹ to R⁸ may bond each other to form a ringstructure;Z includes a divalent group formed by removing two hydrogen atoms fromthe metal complex represented by a following general formula (2′):

wherein L¹ represents a metal coordination part expressed by a followinggeneral formula (3′):

which bonds to Y¹ and Y² in the general formula (1′).

A₁ and A₂ in the general formula (3′) each independently represents asubstituted or unsubstituted aromatic group having 6 to 50 ring carbonatoms and a substituted or unsubstituted aromatic heterocyclic grouphaving 5 to 50 ring atoms, further at least one of A₁ and A₂ is a phenylgroup or a substituted phenyl group. B₁ in the general formula (3′)represents a single bond, —CR′R″—, —SiR′R″—, —CO— or NR′—; R′ and R″each independently represents a hydrogen atom, a substituted orunsubstituted aromatic group having 6 to 50 ring carbon atoms, asubstituted or unsubstituted aromatic heterocyclic group having 5 to 50ring atoms, or a substituted or unsubstituted alkyl group having 1 to 50carbon atoms.

Preferred examples of a metal coordination part represented by thegeneral formula (3′) are as follows.

Among those, a particularly preferable metal coordination part consistsof a following structure:

In the general formula (2′), M represents a metal atom selected from thegroup consisting of Ir, Pt, Os, Re, Pd, Ru, W, Au and Ag, and Ir is apreferred metal atom. In the general formula (2′), [L¹→M] means that L¹cordinates to a metal atom M and that it is selected from the following;

wherein, a carbon atom of L¹ bonds to a metal atom, an atom selectedfrom the group consisting of N, O and S cordinates to a metal atom M.

In the examples of the coordination form, the following coordinationform, in which a carbon atom bonds to a metal atom M and a N atomcordinates to the metal atom M, is preferred.

In the general formula (2′), L² represents a ligand cordinating to ametal and may be the same with or different from L¹; [L²←M] means thatL² cordinates to a metal atom M and that it is selected from a σ-bond ofhalogen atom or the following:

wherein, a carbon atom of L² and an atom selected from O and N bond to ametal atom M and an atom selected from the group consisting of N, O andS cordinates to a metal atom M.

As L², a halogen atom or at least one kind selected from among thosefollowing derivatives including an acetylaceton derivative, an8-quinolinol derivative and a phenylpyridine derivative shown below ispreferable.

In the above, R¹¹ to R²⁷ each independently represents a hydrogen atom,a cyano group, a nitro group, a halogen atom, a substituted orunsubstituted alkyl group having 1 to 20 carbon atoms, alkoxy grouphaving 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbonatoms, or acryl group having 1 to 20 carbon atoms, a substituted orunsubstituted amino group and a substituted or unsubstituted aryl having6 to 30 ring carbon atoms.

It is preferable that L² represents an acetylacetone derivative, an8-quinolinol derivative and a phenylpyridine derivative.

In the general formula (2′), n represents an integer of from 1 to x (x:valence of a metal atom) and m represents an integer of from 0 to (xminus n).

The following shows examples of a compound comprising as least one of astructure of the general formula (1′), but not limited thereto.

The material for an organic EL device of the present invention includesat least one having a compound represented by a following generalformula (4′):(E¹)-(C¹)_(p1)—(C²)_(p2)-(Phos)-(C³)_(p3)—(C⁴)_(p4)-(E²)  (4′).

In the general formula (4′), (Phos) represents a divalent group formedby removing two from among R¹ to R⁸. Z in the general formula (1′)includes preferably one represented by the general formula (2′). E¹ andE² each independently represents a hydrogen atom, or a group selectedfrom among a substituted or unsubstituted aromatic group having ringcarbon atoms of 6 to 50, a substituted or unsubstituted aromaticheterocyclic group having ring atoms of 5 to 50, a substituted orunsubstituted alkyl group having carbon atoms of 1 to 50, a substitutedor unsubstituted alkoxy group having carbon atoms of 1 to 50, asubstituted or unsubstituted aralkyl group having carbon atoms of 7 to50, a substituted or unsubstituted aryloxy group having ring atoms of 5to 50, a substituted or unsubstituted arylthio group having ring atomsof 5 to 50, a substituted or unsubstituted alkoxycarbonyl group havingcarbon atoms of 1 to 50, a carboxyl group, a halogen atom, a cyano groupand a hydroxy group. C¹ to C⁴ each independently represents a groupselected from a substituted or unsubstituted alkylene group having 1 to50 carbon atoms and a substituted or unsubstituted divalent aryl grouphaving 6 to 50 carbon atoms; p1 to p4 each independently represents aninteger of from 0 to 20, preferably from 0 to 5.

Examples of the substituted or unsubstituted aromatic group having 6 to50 ring carbon atoms represented independently by E¹ and E² each includephenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group,2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthrylgroup, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group,1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group,1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group,p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group,m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group,o-tolyl group, m-tolyl group, p-tolyl group, p-t-butylphenyl group,p-(2-phenylpropyl)phenyl group, 3-methyl-2-naphthyl group,4-methyl-1-naphthyl group, 4-methyl-1-anthryl group,4′-methylbiphenyl-yl group, 4″-t-butyl-p-terphenyl-4-yl group, fluorenylgroup, 9,9-dihexylfluorenyl group, 9,9-dioctylfluorenyl group and thelike.

Examples of the substituted or unsubstituted aromatic heterocyclic grouphaving 5 to 50 ring atoms include 1-pyrrolyl group, 2-pyrrolyl group,3-pyrrolyl group, pyradinyl group, pyrimidyl group, pyridazyl group,2-pyridinyl group, group, 3-pyridinyl group, 4-pyridinyl group,1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group,5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group,2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolylgroup, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furylgroup, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group,5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group,1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranylgroup, 5-isobenzofuranyl group, 6-isobenzofuranyl group,7-isobenzofuranyl group, quinolyl group, 3-quinolyl group, 4-quinolylgroup, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolylgroup, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group,5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group,8-isoquinolyl group, 2-quinoxanyl group, 5-quinoxanyl group,6-quinoxanyl group, 1-phenanthridinyl group, 2-phenanthridinyl group,3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinylgroup, 7-phenanthridinyl group, 8-phenanthridinyl group,9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group,2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinylgroup, 1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group,1,7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group,1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group,1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group,1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group,1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group,1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group,1,8-phenanthrolin-9-yl group, 1,8-phenanthrolin-10-yl group,1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group,1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group,1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group,1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group,1,10-phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group,1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group,2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group,2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group,2,9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group,2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group,2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group,2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group,2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group,2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group,2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3-yl group,2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group,2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group,2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group,1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group,2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group,10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group,3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group,2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolylgroup, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group,3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group,2-methylpyrrol-4-yl group, 2-methyl-pyrrol-5-yl group,3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group,3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group,2-t-butylpyrrol-4-yl group, 3-(2-phenylpropyl)pyrrol-1-yl group,2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolylgroup, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group,4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group and4-t-butyl-3-indolyl group and the like.

Examples of the substituted or unsubstituted alkyl group having 1 to 50carbon atoms include methyl group, ethyl group, propyl group, isopropylgroup, n-butyl group, s-butyl group, isobutyl group, t-butyl group,n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group,hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group,2-hydroxyisobutyl group, 1,2-dihydroxyethyl group,1,3-dihydroxy-isopropyl group, 2,3-dihydroxy-t-butyl group,1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group,2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group,1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group,1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group,2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group,1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group,1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group,2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group,1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropylgroup, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group,2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropylgroup, 2,3-diamino-t-butyl group, 1,2,3-triamino-propyl group,cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group,2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropylgroup, 2,3-dicyano-t-butyl group, 1,2,3-tricyano-propyl group,nitromethyl group, 1-nitroethyl group, 2-nitroethyl group,2-nitroisobutyl group, 1,2-dinitroethyl group, 1,3-dinitroisopropylgroup, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group,cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexylgroup, 4-methylcyclohexyl group, 1-adamanthyl group, 2-adamanthyl group,1-norbornyl group, 2-norbornyl group and the like.

The substituted or unsubstituted alkoxyl group having 1 to 50 carbonatoms is a group expressed by —OY. Examples of the group represented byY include methyl group, ethyl group, propyl group, isopropyl group,n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentylgroup, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethylgroup, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutylgroup, 1,2-dihydroxyethyl group, 1,3-dihydroxy-isopropyl group,2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethylgroup, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group,1,2-dichloroethyl group, 1,3-dichloroisopropyl group,2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethylgroup, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group,1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butylgroup, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group,2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group,1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropylgroup, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group,2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropylgroup, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group,cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group,2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropylgroup, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group,nitromethyl group, 1-nitroethyl group, 2-nitroethyl group,2-nitroisobutyl group, 1,2-dinitro-ethyl group, 1,3-dinitroisopropylgroup, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group and thelike.

Examples of the substituted or unsubstituted aralkyl group having 7 to50 carbon atoms include benzyl group, 1-phenylethyl group, 2-phenylethylgroup, 1-phenyl-isopropyl group, 2-phenylisopropyl group, phenyl-t-butylgroup, α-naphthylmethyl group, 1-α-naphthylethyl group,2-α-naphthylethyl group, 1-α-naphthylisopropyl group,2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethylgroup, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group,2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2-(1-pyrrolyl)ethylgroup, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group,p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group,p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group,p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group,p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group,p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group,p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group,p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group,1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group andthe like.

The substituted or unsubstituted aryloxy group having 5 to 50 ring atomsis a group expressed by —OY′. Examples of the group represented by Y′include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthrylgroup, 2-anthryl group, 9-anthryl group, 1-phenanthryl group,2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group,9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group,9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group,2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group,p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group,m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group,o-tolyl group, m-tolyl group, p-tolyl group, p-t-butylphenyl group,p-(2-phenylpropyl)phenyl group, 3-methyl-2-naphthyl group,4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenylylgroup, 4″-t-butyl-p-terphenyl-4-yl group, 2-pyrrolyl group, 3-pyrrolylgroup, pyradinyl group, 2-pyridinyl group, 3-pyridinyl group,4-pyridinyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group,5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group,3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolylgroup, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranylgroup, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group,6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group,3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranylgroup, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolylgroup, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolylgroup, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group,3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group,6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group,2-quinoxanyl group, 5-quinoxanyl group, 6-quinoxanyl group, 1-carbazolylgroup, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group,1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinylgroup, 4-phenanthridinyl group, 6-phenanthridinyl group,7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinylgroup, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group,3-acridinyl group, 4-acridinyl group, 9-acridinyl group,1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group,1,7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group,1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group,1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group,1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group,1,8-phenanthrolin-4-yl group, 1,8-phenanthrolin-5-yl group,1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group,1,8-phenanthrolin-9-yl group, 1,8-phenanthrolin-10-yl group,1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group,1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group,1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group,1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group,1,10-phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group,1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group,2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group,2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group,2,9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group,2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group,2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group,2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group,2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group,2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group,2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3-yl group,2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group,2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group,2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group,1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group,2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group,1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group,4-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolylgroup, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group,2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group,2-methylpyrrol-3-yl group, 2-methylpyrrol-4-yl group,2-methyl-pyrrol-5-yl group, 3-methylpyrrol-1-yl group,3-methyl-pyrrol-2-yl group, 3-methylpyrrol-4-yl group,3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group,3-(2-phenylpropyl)pyrrol-1-yl group, 2-methyl-1-indolyl group,4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolylgroup, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group,2-t-butyl-3-indolyl group, 4-t-butyl-3-indolyl group and the like.

The substituted or unsubstituted arylthio group having 5 to 50 ringatoms is expressed by —SY′ and examples of Y′ include the same asaforementioned.

The substituted or unsubstituted alkoxycarbonyl group having 1 to 50ring carbon atoms is represented by —COOY and examples of Y include thesame as aforementioned.

Examples of the substituted or unsubstituted alkylene group having 1 to50 carbon atoms represented independently by C¹ to C⁴ each includemethylene group, ethylene group, propylene group, isopropylene group,n-butylene group, s-butylene group, isobutylene group, dimetylmethylenegroup, n-pentylene group, n-hexylene group, n-heptylene group,n-octylene group, chloromethylene group, 1-chloroethylene group,2-chloroethylene group, 2-chloroisobutylene group, 1,2-dichloroethylenegroup, 1,3-dichloroisopropylene group, 1,2,3-trichloropropylene group,bromomethylene group, 1-bromoethylene group, 2-bromoethylene group,2-bromoisobutylene group, 1,2-dibromoethylene group,1,3-dibromoisopropylene group, 1,2,3-tribromopropylene group,iodomethylene group, 1-iodoethylene group, 2-iodoethylene group,2-iodoisobutylene group, 1,2-diiodoethylene group,1,3-diiodoisopropylene group, 1,2,3-triiodopropylene group,cyclopropylene group, cyclobutylene group, cyclopentylene group,cyclohexylene group, 4-methylenecyclohexylene group, adamantane-1,1-diylgroup, adamantane-1,3-diyl group and the like.

Examples of a substituted or unsubstituted divalent arylene havingcarbon atoms of 6 to 50 represented independently by C¹ to C⁴ eachinclude the following.

Examples of a compound represented by the general formula (4′) are shownas follows, but not limited thereto.

Further, a material for an organic EL device of the present inventionincludes a material containing a following polymer A or a followingpolymer B.

The polymer A comprises a polymer formed by polymerizing orcopolymerizing a compound represented by the general formula (1′), andat least one among R¹ to R⁸ of the formula (1′) is an aromatic grouphaving ring carbon atoms of 6 to 50 containing a polymerizable group ora copolymerizable group. A polymerizable group includes a vinyl group,an epoxy group and the like, preferably a vinyl group.

The following shows examples of the polymer A, but not limited thereto.

A copolymerizable comonomer includes a compound having a polymerizablevinyl group. The following is preferable compounds having apolymerizable vinyl group. In addition, plural comonomer thereof, ifrequired, may be copolymerized.

Examples of the copolymers are shown as follows, but not limitedthereto.

The polymer B comprises a polymer or a copolymer containing a unitstructure of a divalent group formed by removing two selected from amongR¹ to R⁸ in the general formula (1′). The following is example of theunit structure:

A copolymerizable comonomer includes preferably a substituted orunsubstituted divalent aromatic group having ring carbon atoms 6 to 50,a substituted or unsubstituted divalent aromatic heterocyclic grouphaving ring carbon atoms of 5 to 50, and a divalent triarylaminederivative having carbon atoms of 18 to 50, and further plural comonomerthereof may be copolymerized. Moreover, followings are preferablecomonomer units.

Molecular weight of the polymer A or the polymer B is preferably 1,000to 3,000,000, more preferably 1,000 to 1,000,000. Examples of thepolymer B including the copolymer are shown as follows, but not limitedthereto.

Following is a description regarding a device structure about theorganic EL device of the present invention.

The present invention provides an organic EL device which comprises atleast one organic thin film layer sandwiched between a pair ofelectrodes consisting of an anode and a cathode, wherein at least oneorganic thin film layer comprises the foregoing coordination metalcompound or the foregoing material for the organic EL device.

Typical examples of the construction of the organic EL device of thepresent invention include:

(1) An anode/a light emitting layer/a cathode;

(2) An anode/a hole injecting layer/a light emitting layer/a cathode;

(3) An anode/a light emitting layer/an electron injecting layer/acathode;

(4) An anode/a hole injecting layer/a light emitting layer/an electroninjecting layer/a cathode;

(5) An anode/an organic semiconductor layer/a light emitting layer/acathode;

(6) An anode/an organic semiconductor layer/an electron barrier layer/alight emitting layer/a cathode;

(7) An anode/an organic semiconductor layer/a light emitting layer/anadhesion improving layer/a cathode;

(8) An anode/a hole injecting layer/a hole transporting layer/a lightemitting layer/an electron injecting layer/a cathode;

(9) An anode/an insulating layer/a light emitting layer/an insulatinglayer/a cathode;

(10) An anode/an inorganic semiconductor layer/an insulating layer/alight emitting layer/an insulating layer/a cathode;

(11) An anode/an organic semiconductor layer/an insulating layer/a lightemitting layer/an insulating layer/a cathode;

(12) An anode/an insulating layer/a hole injecting layer/a holetransporting layer/a light emitting layer/an insulating layer/a cathode;and

(13) An anode/an insulating layer/a hole injecting layer/a holetransporting layer/a light emitting layer/an electron injecting layer/acathode.

However, the construction of the organic EL device is not limited tothose shown above as the examples.

It is preferable, but not limited thereto, for the organic EL device ofthe present invention to employ the material of the present invention asa constituting material for the light emitting layer. In the case ofthat the compound having a spiro bond of the present invention isemployed in the light emitting layer, the compound can be usually usedwith various organic materials employed for the organic EL device incombination. It is particularly preferable to employ an amine compoundhaving a styryl group or an arylamine compound as a dopant.

In general, it is preferable that the organic EL device is fabricated ona substrate which transmits light. It is preferable that the substratewhich transmits light has a transmittance of light of 50% or greater inthe visible region of 400 to 700 nm. It is also preferable that a flatand smooth substrate is employed.

As the substrate which transmits light, for example, glass sheet andsynthetic resin sheet are advantageously employed. Specific examples ofthe glass sheet include soda ash glass, glass containing barium andstrontium, lead glass, aluminosilicate glass, borosilicate glass, bariumborosilicate glass and quartz. Specific examples of the synthetic resinsheet include sheet made of polycarbonate resins, acrylic resins,polyethylene terephthalate resins, polyether sulfide resins andpolysulfone resins.

The anode in the organic EL device of the present invention covers arole of injecting holes into a hole transport layer or into a lightemitting layer, and it is effective that the anode has a work functionof 4.5 eV or greater. Specific examples of the material for the anodeinclude indium tin oxide (ITO) alloy, tin oxide (NESA), gold, silver,platinum, copper, etc. With regard to the cathode, it is preferable thata material has a small work function with the objective of injectingelectrons into an electron transport layer or into a light emittinglayer.

The anode can be prepared by forming a thin film of the electrodematerial described above in accordance with a process such as a vapordeposition process or a sputtering process.

When the light emitted from the light emitting layer is observed throughthe anode, it is preferable that the anode has a transmittance of theemitted light greater than 10%. It is also preferable that the sheetresistivity of the anode is several hundred Ω/□ or smaller. Thethickness of the anode is, in general, selected in the range of from 10nm to 1 μm and preferably in the range of from 10 to 200 nm.

It is preferable that an organic device of the present invention has ahole transporting layer between the light emitting layer and the anode,and the hole transporting layer contains an arylamine derivative as anessential component. In addition, a hole transporting material to becontained in a hole transporting layer has preferably a triplet energyof 2.52 to 3.7 eV, more preferably 2.8 to 3.7 eV. By using a holetransporting material in the range of the above, it is possible to avoiddeactivation of excitation energy of a light emitting layer.

The hole transportation material includes preferably a materialrepresented by the general formulae (A) and (B):

wherein, Ar⁷ represents an aromatic group having carbon atoms of 6 to40, Ar⁸ and Ar⁹ each independently represents a hydrogen atom or anaromatic group having carbon atoms of 6 to 40, and m represents aninteger of from 1 to 6.

wherein, Ar¹⁰ and Ar¹⁶ each independently represents an aromatic grouphaving carbon atoms of 6 to 40, Ar¹¹ to Ar¹⁵ each independentlyrepresents a hydrogen atom or an aromatic group having carbon atoms of 6to 40, and a condensation numbers of p, q, r and 8 each independentlyrepresents an integer of from 0 to 1.

In the general formulae (A) and (B), the preferable aryl group having 5to 40 ring carbon atoms among the aromatic hydrocarbon groups havingring carbon atoms of 6 to 40 is a phenyl group, a naphthyl group, ananthranyl group, a phenanthryl group, a pyrenyl group, a coronyl group,a biphenyl group, a terphenyl group, a pyrrolyl group, a furanyl group,a thiophenyl group, a benz thiophenyl group, an oxadiazolyl group, adiphenyl anthranyl group, an indolyl group, a carbazolyl group, apyridyl group, a benzoquinolyl group, a fluoranthenyl group, anacenaphthofluoranthenyl group and the like. In addition, preferableexamples of the arylene group having carbon atoms of 5 to 40 include aphenylene group, a naphthylene group, an anthranylene group,phenanthrylene, a pyrenylene group, colonylene group, a biphenylenegroup, a terphenylene group, a pyrrolylene group, a furanylene group, athiophenylene gorup, a benzothiophenylene group, an oxadiazolylenegroup, a diphenylanthranylene, an indolylene group, a carbazolylenegroup, a pyridilene group, a benzoquinolilene group, a fluolanthenylenegroup, acenaphthofluoranthenylene and the like. Moreover, an aromaticgroup having carbon atoms of 6 to 40 may be substituted by asubstituent, and a preferable substituent includes an alkyl group havingcarbon atoms of 1 to 6 such as ethyl group, methyl group, i-propylgroup, n-propyl group, s-butyl group, t-butyl group, pentyl group, hexylgroup, cyclopentyl group and cyclohexyl group, an alkoxy group havingcarbon atoms of 1 to 6 such as ethoxy group, methoxy group, i-propoxygroup, n-propoxy group, s-butoxy group, t-butoxy group, pentoxy group,hexyloxy group, cyclopentoxy group, cylcohexyloxy group, an aryl grouphaving ring carbon atoms of 5 to 40, an amino group substituted by anaryl group having ring carbon atoms of 5 to 40, an ester group having anaryl group having ring carbon atoms of 5 to 40, an ester group having analkyl group having carbon atoms of 1 to 6, a cyano group, a nitro groupand a halogen atom.

In addition, a hole transporting material having triplets energy of 2.8eV or larger includes preferably a material represented by followinggeneral formulae (C) to (E).

wherein, Ar¹ and Ar² each independently represents an alkyl group havingcarbon atoms of 1 to 6 and an aryl group having ring carbon atoms of 6to 18 which may be substituted by an alkoxy group or a phenyl group, andR represents an alkyl group or an alkoxy group having carbon atoms of 4to 6, or an aryl group having ring carbons of 6 to 18; X represents asingle bond or an interconnection group represented by —O— or —S—, whichmay exist or not.

wherein, Ar³ represents an aryl group having ring carbon atoms of 6 to18, which may be substituted; Ar⁴ to Ar⁷ each respectively representsarylene group having ring carbon atoms of 6 to 18, which may besubstituted; X¹ represents a single bond or an interconnection bond of—O—, —S—, —(CH₂)_(n)— (n represents an integer of from 1 to 6) or—C(CH₃)₂— and the interconnection bond may exist or not; X² and X³ eachindependently represents a single bond, an connection bond of —O—, —S—,—(CH₂)_(n)—, n represents an integer of from 1 to 6 or —C(CH₃)₂—, andthese may be the same with or different from each other.

In the general formulae (C) and (D), specific examples represented byeach group and each substituent of Ar¹ to Ar⁷, R, X and X¹ to X³includes the same as aforementioned about Ar¹ to Ar⁶.

wherein, R¹ to R¹² each independently represents a hydrogen atom, ahalogen atom, an alkyl group, an aralkyl group, an alkenyl group, acyano group, an amino group, an acryl group, an alkoxycarbonyl group, acarboxyl group, an alkoxy group, an alkylamino group, an aralkylaminogroup, a haloalkyl group, a hydroxyl group, an aryloxy group, and anaromatic hydrocarbon ring group and an aromatic heterocyclic group whichmay be substituted, both R¹ and R², both R³ and R⁴, both R⁵ and R⁶, bothR⁷ and R⁸, both R⁹ and R¹⁰, and both R¹¹ and R¹² each independently mayform a ring of neighboring groups thereof; X represents a trivalentinterconnection group as follows:

and Ar¹ is expressed by any one of an aromatic hydrocarbon ring groupwhich may be substituted, an aromatic heterocyclic group which may besubstituted or the general formula (F):

wherein, R¹³ to R¹⁸ each independently represents a hydrogen atom, ahalogen atom, an alkyl group, an aralkyl group, an alkenyl group, acyano group, an amino group which may be substituted, an acryl group, analkoxycarbonyl group, a carboxyl group, an alkoxy group, an alkylaminogroup, an aralkylamino group, a haloalkyl group, a hydroxyl group, anaryloxy group, and an aromatic hydrocarbon ring group and an aromaticheterocyclic group which may be substituted, both R¹³ and R¹⁴, both R¹⁵and R¹⁶, and both R¹⁷ and R¹⁸ each independently may form a ring ofneighboring groups thereof. In the general formula (F), specificexamples of each group and substituent represented by R¹³ to R¹⁸ includethe same as aforementioned about Cz and Ar¹ to Ar⁶.

In the organic EL device of the present invention, a hole transportationlayer is explained as aforementioned. In addition, an organic EL deviceof the present invention may has a further hole transportation layer. Asa material for the further hole transportation layer, a material whichtransports holes to the light emitting layer at a small strength of theelectric field is preferable. A material which exhibits, for example, amobility of holes of at least 10⁻⁴ cm²/V·sec under application of anelectric field of from 10⁴ to 10⁶ V/cm is preferable. Any arbitrarymaterial selected from conventional material commonly used as a chargetransporting material for the holes in photo conducting materials andwell known material employed for the hole injecting layer in the ELdevice is usable.

As an hole injecting material, it is preferable that a compound has ahole transporting capabilit6y, a hole injecting effect from an anode, aexcellent hole injecting effect to a light emitting layer or a lightemitting material, and it has a prevention ability of excitons formed inthe light emitting layer from transferring to an electron injectinglayer or an electron injecting material and an excellent ability forminga thin film. Specific examples thereof include a phthalocyaninederivative, a naphthalocyanine derivative, a porphyrine derivative,oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolthion,pyrazoline, pyrazolone, tetrahydroimidazole, hydrazone, acylhydrazone,polyarylalkane, stilbene, butadiene, benzidine-base triphenylamine,styrylamine-base triphenylamine, diamine-base triphenylamine,diamine-base triphenylamine and the like, derivatives thereof, andpolymer materials such as polyvinyl carbazole, polysilane, polyethylenedioxythiophene, polystyrene sulfonate, electroconductive polymer, butnot to limited thereto.

Among the hole injecting materials, a further effective hole injectingmaterial includes a aromatic tertiary amine derivative or aphthalocyanine derivative. Specific examples of aromatic tertiary amineinclude, triphenylamine, tritolylamine, tolyldiphenylamine,N,N′-diphenyl-N,N′-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine,N,N,N′,N′-(4-methylphenyl)-1,1′-phenyl-4,4′-diamine,N,N,N′,N′-(4-methylphenyl)-1,1′-biphenyl-4,4′-diamine,N,N′-diphenyl-N,N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine,N,N′-(methylphenyl)-N,N′-(4-n-butylphenyl)-phenanthrene-9,10-diamine,N,N′-bis(4-di-4-tolylaminophenyl)-4-phenyl-cyclohexane and the like, oroligomer or polymer having an aromatic tertiary amine skeleton structurethereof, but not limited thereto. Specific examples of a phthalocyaninederivative (Pc) include a phthalocyanine derivative such as H₂Pc, CuPc,CoPc, NiPc, ZnPc, PDPC, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc,Cl₂SiPc, (HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc-O—GaPc and anaphthalocyanine derivative, but not limited thereto.

For forming the hole injecting/transporting layer, a well known processsuch as the vapor deposition process, the spin coating process and theLB process can be employed so as to form a thin film of theaforementioned compounds. Although a film thickness for the holeinjecting/transporting layer is not limited, it is generally 5 nm to 5μm. The hole injecting/transporting layer may be constructed by a layercomprising at least one of the aforementioned materials or by laminatinga hole injecting/transporting layer comprising a different compoundother than the aforementioned hole injecting/transporting layer.

In addition, an organic semiconductor layer is to help hole injection orelectron injection into a light emitting layer, and a electricconductivity of 10⁻¹⁰ S/cm or greater thereof is preferable. With regardto a material for the organic semiconductor layer, an electroconductiveoligomer such as an oligomer having thiophene, an oligomer havingarylamine disclosed in Japanese Unexamined Patent Application Laid-OpenNo. 8-193191 and the like, electroconductive dendrimers such as adendrimer having an arylamine dendrimer and the like are employable.

In the organic EL device of the present invention, the light emittinglayer has the following functions:

(1) The injecting function: the function of injecting holes from theanode or the hole injecting layer and injecting electrons from thecathode or the electron injecting layer when an electric field isapplied;

(2) The transporting function: the function of transporting injectedcharges (electrons and holes) by the force of the electric field; and

(3) The light emitting function: the function of providing the field forrecombination of electrons and holes and leading the recombination tothe light emission. Although there may be a difference between thecapability of the holes being injected and the capability of theelectrons being injected, and although there may be a grade about thetransporting function expressed by mobility of the holes and theelectrons, it is preferable to move charges of either ones.

As the process for forming the light emitting layer, a well knownprocess such as the vapor deposition process, the spin coating processand the LB process can be employed.

In the present invention, any well known light emitting material such asPVK, PPV, CBP, Alq, BAlq and a well known complex other than the lightemitting material comprising a coordination metal compound of thepresent invention or a light emitting material explained below may beoptionally contained in the light emitting layer in an extent of notobstructing to achieve the objective of the present invention. Further,a compound of the present invention may be used without having a metalatom cordinated, and also such compound may be used together, as amixture, with a compound of the present invention having a metal atomcordinated.

A compound to be contained in the light emitting layer includes, forexample, a structure such as any of following general formulae (L1) to(L22). In addition, in the following structures, a phenyl part and athiophene part include one substituted by an alkyl group or an arylgroup having carbon atoms of 6 to 10.

In the above general formulae, Cz includes a carbazolyl group, anarylacrbazoleyl group having carbon atoms of 16 to 60, an azacarbazolylgroup, an arylazacarbazoleyl having carbon atoms of 18 to 60 group, anacridinyl group, a phenoxadinyl group or a dibenzoazevinyl group, whichmay be substituted. Ar¹ and Ar² each independently represents asubstituted or unsubstituted aryl group having ring carbon atoms of 6 to60 or a substituted or unsubstituted heterocyclic group having carbonatoms of 3 to 60.

Further, a light emitting material expressed by the general formulae(L1) to (L22) includes following compounds.

Moreover, those compounds are preferable to be a host material andtransporting electric charge, and its glass transition temperature is110° C. or higher. In addition, if triplet energy thereof is 2.76 eV orgreater, it is preferable that they have a capability of exciting acomplex emitting a green light and a red light. Furthermore, thesecompounds have a glass transition temperature of 110° C. or higher andtriplets energy of 2.82 eV or greater, and it is possible for them tohave triplets energy of 2.85 eV or greater so that they are excellent instorage at elevated temperature and possible to improve an efficiency oflight emission of a green light emitting device in comparison with thatof CBP. In addition, so as to excite a complex emitting a green lightand a red light, the triplet energy thereof of 2.82 to 2.92 eV ispreferable.

In an organic EL device of the present invention, in the case of that ahost material of a light emitting layer thereof having triplet energy of2.76 eV or greater, it is preferable that a capability of emitting bluelight is high, and further 2.85 eV or greater thereof is morepreferable.

Further, it is preferable that a host material of the light emittinglayer has electron transporting ability. In the present invention, “ahost material of the light emitting layer has electron transportingability” means either an item (1) below or an item (2) below:

(1) An electron mobility of the host material in the light emittinglayer is 10⁻⁶ cm²/Vs or greater. The electron mobility can be measuredby a time-of-flight method (TOF) or “transient measurement of spacecharge limited current”. For references, TOF method is described insynthetic metals 111/112, (2000) p133, and “transient measurement ofspace charge limited current” is described in Electrical Transport inSolids, Pergamon Press, 1981, pages 346-348.

(2) Recombination between holes and electrons in zone of an anode sidein a light emitting layer is caused easier than recombination betweenthem in zone of a cathode therein. In the case of that a layerconstruction is constituted by “a cathode/an electron injecting layer atan anode side/a light emitting layer at a cathode side/a holetransporting layer/an anode” by dividing the zone of the light emittinglayer in two, and a device AN comprised by a light emitting layer at ananode side, only to which a phosphorescent luminescent compound is addedis compared with a device CA comprised by a light emitting layer at acathode side, only to which a phosphorescent luminescent compound isadded so that it is the case that an efficiency of light emission of thedevice AN is higher than that of the device CA. In the above case, itshould be noted that a excited state is not to be quenched optically bythe electron injecting layer or the hole transporting layer.

In addition, the electron transporting ability does not mean that thereis no hole transporting ability. Therefore, although it has a electrontransporting ability, it is the case that it has a electron transportingability even at the measured hole mobility of 10⁻⁷ cm²/Vs or more.

In the past, a polycarbazole compound such as polyvinylcarbazole,biscarbazole and the like has generally a hole transportability,therefore an electron transportability is small. In the case of thatthese materials having a hole transportability is used as a hostmaterial, a main recombination zone is around interfacial zone of acathode side in a light emitting layer. In this case, a excited stateoccurred mainly around the interfacial zone of the cathode side in thelight emitting layer is deactivated and the efficiency thereof becomesvery low, in the case of that an electron transporting material having asmaller energy gap than an energy gap of a host material constituting alight emitting layer is contained in an electron injecting layer byplacing the electron injecting layer between the light emitting layerand the cathode. Further, even though the triplet energy of an electronmaterial forming an electron injecting layer is smaller than the tripletenergy of a host material forming a light emitting layer, a excitedstate occurred mainly around the interfacial zone of the cathode side inthe light emitting layer is deactivated by the electron injection layerand the efficiency thereof becomes very low.

On the other hand, in the case of that a host material forming a lightemitting layer is to be an electron transportability or a light emittinglayer is to be an electron transportability, a recombination zone of anelectron and a hole is apart from an interfacial zone between theelectron injecting layer and the light emitting layer so thatdeactivation thereof can be avoided. In addition, in the presentinvention, a preferable host material for a light emitting material is a5 member derivative containing nitrogen or a 6 member derivativecontaining nitrogen which are electron deficiency. Here, the electrondeficiency means a derivative, of which, for example, one or more ofcarbon for a 6 π aromatic ring is replaced by nitrogen.

The 5 member derivative containing nitrogen includes preferably aderivative having at least a skeleton structure selected from imidazole,benzimidazole, triazole, tetrazole, oxadiazole, thiadiazole, oxatriazoleand thiatriazole, and, a derivative having a skeleton structure ofimidazole or benzimidazole is more preferable.

The 6 member derivative containing nitrogen includes preferably aderivative having at least a skeleton structure selected from triazine,quinoxaline, benzpyrimidine, pyridine, pyrazine and pyrimidine, and aderivative having a skeleton structure of triazine or pyrimidine is morepreferable.

A preferable host material in the light emitting layer is particularly amaterial represented by the general formulae (G) and (H):(Cz-)_(m)A  (G)wherein, Cz represents a substituted or unsubstituted carbazole group,or a substituted or unsubstituted azacarbazole group; A represents anitrogen containing ring group substituted by an aryl group, a nitrogencontaining ring group substituted by a diaryl group, or a nitrogencontaining ring group substituted by a triaryl group; m represents aninteger of from 1 to 3.

Cz-A_(n)  (H)

wherein, Cz represents a substituted or unsubstituted carbazole group,or a substituted or unsubstituted azacarbazole group; A represents anitrogen containing ring group substituted by an aryl group, a nitrogencontaining ring group substituted by a diaryl group, or a nitrogencontaining ring group substituted by an triaryl group; n represents aninteger of from 1 to 3.

In the general formulae (G) and (H), a preferable nitrogen containingring includes pyridine, quinoline, pyrazine, pyrimidine, quinoxaline,triazine, imidazoline and imidazopyridine.

Further, in the general formulae (G) and (H), an ionization potentialvalue is subjected to Cz, and the value is from 5.6 eV to 5.8 eV.

The preferable organic EL device comprises an electroninjecting/transporting layer between the light emitting layer and thecathode and the electron injecting/transporting layer contains nitrogencontaining ring derivative as the main component. An electrontransporting material to be used for the electron injecting/transportinglayer includes preferably an aromatic heterocyclic compound having atleast one of a hetero atom therein, more preferably a nitrogencontaining ring derivative. The nitrogen containing ring derivative ispreferably a derivative having an azole skeleton structure of a 5 memberring. The aromatic hetero compound means its compound having at leasttwo atoms other than a carbon atom and a hydrogen atom within the basicskeleton structure thereof, and it may be a single ring or a condensedring. The nitrogen containing ring derivative includes preferably itsderivative having at least one atom selected from a nitrogen atom, anoxygen atom and a sulfur atom, and also includes more preferably anaromatic heterocyclic ring having at least two of nitrogen atoms withinthe skeleton structure thereof. The hetero atom may be located at acondensed part or a non-condensed part. The heterocyclic skeletonstructure having at least two hetero atoms includes, for example,pyrazole, imidazole, pirazine, pyrimidine, indazole, purine,phthalazine, naphthylidine, quinoxaline, quinazoline, cinnoline,pteridine, perimidine, phenanthroline, pyrroimidazole, pyrootriazole,pyrazoloimidazole, purazolotriazole, pyrazolopyrimidine,pyrazolotriazine, imidazoimidazole, imidazopyridazine, imidazopyridine,imidazopyrazine, triazopyridine, benzoimidazole, naphtoimidazole,benzoxazole, naphtoxazole, benzothiazole, naphtothiazole, benzotriazole,tetrazaindene, triazine and the like.

Among the above, the electron transportable host material includespreferably a compound thereof having a condensed azole skeletonstructure such as imidazopyridazine, imidazopyridine, imidazopyrazine,benzoimidazole and aphtoimidazole, or a compound having a triazineskeleton structure, and more preferably condensed imidazopyridine.

A compound having the azole skeleton structure is preferably representedby the general formula (J):

wherein, R represents an aromatic group, X represents O, S or N-Ra; Rarepresents a hydrogen atom, a aliphatic hydrocarbon group, an aryl groupor a heterocyclic group; Q represents an atom group which is requiredfor forming a heterocyclic ring by bonding with N and X. Further, both Rand X, and both R and Q may bond each other to form a ring if possible.

The preferable nitrogen containing ring derivative includes thefollowing:

On the other hand, an electron transporting material includes thefollowing oxazole derivatives:

wherein, Ar¹, Ar², Ar³, Ar⁵, Ar⁶ and Ar⁹ each independently represents asubstituted or unsubstituted aryl group, and may be the same with ordifferent from each other. Further, Ar⁴, Ar⁷ and Ar⁸ each independentlyrepresents a substituted or unsubstituted aryl group, and may be thesame with or different from each other.

Here, the aryl group includes a phenyl group, a biphenyl group, ananthranyl group, a perylenyl group, a pyrenyl group and the like. Inaddition, the arylene group includes a phenylene group, a naphtylenegroup, a biphenylene group, a perylenylene group, a pyrenylene group andthe like. Moreover, the substituent includes an alykyl group havingcarbon atoms of 1 to 10, an alkoxy group having carbon atoms of 1 to 10a cyano group or the like. The electron transporting compound includespreferably a compound having a film forming capability.

Specific examples of the electron transporting compound include thefollowing:

In addition, a nitrogen containing complex is preferable as the electrontransporting material, and the nitrogen containing complex includes ametal complex cordinated by a single species of a nitrogen ringderivative, and the nitrogen containing ring is preferably quinoline,phenylpyridine, benzoquinoline or phenanthroline. Further, it ispreferable that the metal complex is a quinolinol metal complex or aderivative thereof. Specific examples of a metal complex having a8-quinolinol derivative as a ligand include tris(8-quinolinol) Alcomplex, tris(5,7,-dichloro-8-quinolinol) Al complex,tris(5,7-dibromo-8-quinolinol) Al complex, tris(2-methyl-8-quinolinol)Al complex, tris(8-quinilinol) Zn complex, tris(8-quinolinol) Incomplex, tris(8-quinolinol) Mg complex, tris(8-qunolinol) Cu complex,tris(8-quinolinol) Ca complex, tris(8-quinolinol) Sn complex,tris(8-quinolinol) Ga complex, tris(8-quinolinol) Pb complex and thelike, and they are used alone or in combination of at least two selectedfrom among them.

Those complexes have an excellent electron injection capability from acathode due to small energy gap thereof and high durability aboutelectron transportation; therefore provide a device having a longlifetime.

Specific examples of these metal complexes are as follows.

In addition, it is preferable that an insulating material or asemiconductor of an inorganic compound other then the electrontransportable materials is used as a constituent component for theelectron injecting layer. It is possible to effectively prevent anelectron injecting layer from leak of the electric current and improvethe electron injecting capability when the layer is constituted with asemiconductor or an inorganic compound.

It is preferable that at least one metal compound selected from thegroup consisting of alkali metal chalcogenides, alkaline earth metalchalcogenides, alkali metal halides and alkaline earth metal halides isused as the insulating material. It is preferable that the electroninjecting layer is constituted with the above alkali metal chalcogenidesince the electron injecting capability can be improved. Preferableexamples of the alkali metal chalcogenide include Li₂O, LiO, Na₂S, Na₂Seand NaO. Preferable examples of the alkaline earth metal chalcogenideinclude CaO, BaO, SrO, BeO, BaS and CaSe. In addition, preferableexamples of the alkali metal halide include LiF, NaF, KF, LiCl, KCl andNaCl. Further, preferable examples of the alkaline earth metal halideinclude fluorides such as CaF2, Ba F₂, Sr F₂, Mg F₂ and Be F₂, andhalides other than the fluorides.

Moreover, examples of the semiconductor constituting the electrontransporting layer include oxides, nitrides and oxide nitridescontaining at least one element selected from the group consisting ofBa, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn, which canbe used alone or in combination of two or more kind thereof. It is alsopreferable that the inorganic compound constituting the electrontransporting layer is in the form of an insulating thin film of finecrystalline or amorphous. When the electron transporting layer isconstituted with the above insulating thin film, a more uniform thinfilm can be formed so that defective pixels such as dark spots can bedecreased. Examples of the inorganic compound include the alkali metalchalcogenides, the alkaline earth metal chalcogenides, the alkali metalhalides and the alkaline earth metal halides which are described above.

In the organic EL device of the present invention, it is preferable thata reductive dopant is added in an interfacial zone between the cathodeand the organic thin film layer.

Examples of the reductive dopant include at least one compound selectedfrom alkali metals, alkali metallic complexes, alkali metal compounds,alkaline earth metals, alkaline earth metallic complexes, alkaline earthmetal compounds, rare earth metals, rare earth metallic complexes andrare earth metal compounds, and also oxides, halides and the like of theabove metals or complexes. Examples of the alkali metals include L1 (thework function: 2.93 eV), Na (the work function: 2.36 eV), K (the workfunction: 2.28 eV), Rb (the work function: 2.16 eV), Cs (the workfunction: 1.95 eV) and the like, whose work function of 3.0 eV orsmaller is particularly preferable. Among these, Li, K, Rb and Cs aremore preferable.

Examples of the alkaline earth metals include Ca (the work function: 2.9eV), Sr (the work function: 2.0 to 2.5 eV) and Ba (the work function:2.52 eV); whose work function of 3.0 eV or smaller is particularlypreferable. The alkaline earth metals include Sc, Y, Ce, Tb, Yb and thelike, whose work function of 3.0 eV or smaller is particularlypreferable.

Since a preferable metal among the above metals has particularly highreduction power, it is possible to improve luminance of emitted light ofthe organic EL device and to provide it with a long lifetime throughadding a small amount the metal into an electron injection zone.

Examples of the alkali metal compound include an alkali metal oxide suchas Li₂O, Cs₂O and K₂O and an alkali metal halide such as LiF, NaF, CsFand KF, and an alkali metal oxide or an alkali fluoride such as LiF,Li₂O and NaF is preferable.

Examples of the alkaline earth metal compound include BaO, CaO, SrO,Ba_(x)Sr_(1-x)O (0<x<1) and Ba_(x)Ca_(1-x)O (0<x<1) obtained by mixingthem, and the like, further, BaO, SrO and CaO are preferable.

Examples of the rare earth metal include YbF₃, ScF₃, ScO₃, Y₂O₃, Ce₂O₃,GdF₃, TbF₃ and the like, and YbF₃, ScF₃ and TbF₃ are preferable.

There is no specific limitation if at least one selected from the groupconsisting of an alkali metal ion, an alkaline earth metal ion and arare earth metal for the alkali metal complex, the alkaline earth metalcomplex and the rare earth metal complex, is contained therein.

In addition, as the ligand, quinolinol, benzoquinolinol, acrydinol,phenanthridinol, hydroxyphenyloxazole, hydroxyphenylthiazoole,hyddroxydiaryloxazole, hydroxydiarylthiadiazole, hydroxyphenylpyridine,hydroxyphenylbenzoimidazole, hydroxybenzotriazole, hydroxyfluborane,bipyridyle, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene,β-diketone, azomethines and derivatives thereof, but not limitedthereto.

As an addition manner of the reductive dopant, it is preferable to formit in a layer shape or in an island shape at the interfacial zone.

As a forming process thereof, it is preferable that organic materials ofa light emitting material or an electron injecting material forming aninterfacial zone are deposited while depositing a reductive dopant by aresistive heating vapor deposition process and the reductive dopant isdispersed into the organic materials. The dispersion concentration is anorganic material: a reductive dopant=100:1 to 1:100, preferably 5:1 to1:5 by mole ratio.

When forming the reductive dopant in a layer shape, a light emittingmaterial or an electron injecting material is formed in a layer shape,followed by depositing the reductive dopant alone by a resistive heatingvapor deposition process so as to form the layer having preferably athickness of 0.1 to 15 nm.

When forming the reductive dopant in a island shape, a light emittingmaterial or an electron injecting material of an organic layer at theinterface is formed in a island shape, followed by depositing thereductive dopant singly by a resistive heating vapor deposition processso as to form the layer having preferably a thickness of 0.1 to 15 nm.

The ratio by mole between the main component and the reductive dopant ofthe organic EL devices of the present invention is the main component:the reductive dopant=5:1 to 1:5 preferably 2:1 to 1:2. In the organic ELdevice, an electrode material for a cathode comprised a metal, an alloy,an electroconductive compound and a mixture thereof having a small workfunction can be used.

Specific examples of such electrode material include sodium,sodium-potassium alloy, magnesium, lithium, magnesium-silver alloy,aluminum/aluminum oxide, aluminum/lithium alloy, indium, rare earthmetals and the like.

The cathode is produced by forming a thin film through deposition,sputtering and the like of these electrodes. When the light emitted fromthe light emitting layer is observed through the cathode, it ispreferable that the cathode has a transmittance of the emitted lightgreater than 10%. It is also preferable that the sheet resistivity ofthe cathode is several hundred Ω/□ or smaller. The thickness of thecathode is, in general, selected from the range of from 10 nm to 1 μmand preferably from the range of from 10 to 200 nm.

The organic EL device of the present invention tends to cause defects inpixels due to leak and short circuit since an electric field is appliedto ultra-thin films. To prevent the formation of the defects, a layer ofan insulating thin film may be inserted between the pair of electrodes.

Examples of the material employed for the insulating layer includealuminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesiumoxide, magnesium oxide, magnesium fluoride, calcium oxide, calciumfluoride, aluminum nitride, titanium oxide, silicon oxide, germaniumoxide, silicon nitride, boron nitride, molybdenum oxide, rutheniumoxide, vanadium oxide and the like. In addition, mixtures and laminatesof the above compounds can be employed.

The process for forming the layers in the organic EL device of thepresent invention is not particularly limited. A conventional processsuch as the vacuum vapor deposition process, the spin coating processand the like can be used. The organic thin film layer comprising thecompound having a spiro bond represented by the aforementioned generalformula (1) or (1′) used in the organic EL device of the presentinvention can be formed in accordance with the vacuum vapor depositionprocess, the molecular beam epitaxy process (the MBE process) or, usinga solution prepared by dissolving the compound into a solvent, inaccordance with a conventional coating process such as the dippingprocess, the spin coating process, the casting process, the bar coatingprocess and the roller coating process.

The thickness of each layer in the organic thin film layer in theorganic EL device of the present invention is not particularly limited.In general, the range from several nm to 1 μm in thickness thereof ispreferable, since an excessively thin layer tends to have defects suchas pin holes, and an excessively thick layer requires a high appliedvoltage results in decreasing the efficiency.

The coordination metal compounds of the present invention have afavorable solubility to organic solvents due to a spiro atomic group ora carbazoyl group thereof. Accordingly, the compounds of the presentinvention having a high molecular weight and difficulty of thin filmproduction by the vacuum vapor deposition can be easily formed to be thethin film by means of any application process such as the dippingprocess, the spin coating process, the casting process, the bar coatingprocess, the roller coating process and the like. The material forluminescent coating formation of the present invention essentiallyconsists of an organic solvent comprising the coordination metalcompound. The material for luminescent coating formation is defined as amaterial for providing an organic compound layer relating to lightemission, specifically a light emitting layer, hole injecting(transporting) layer, electron injecting (transporting) layer, and so onby means of forming a coated film in the organic EL device.

Examples of the organic solvent used for preparation of the material forluminescent coating formation include, halogen-based hydrocarbon solventsuch as dichloro-methane, dichloroethane, chloroform,tetrachloromethane, tetrachloro ethane, trichloroethane, chlorobenzene,dichlorobenzene, chlorotoluene, etc.; ether-based solvent such asdibutyl ether, tetrahydrofuran, dioxane, anisole, etc.; alcohol-basedsolvent such as methanol, ethanol, propanol, butanol, pentanol, hexanol,cyclohexanol, methyl cellosolve, ethylcellosolve, ethylene glycol, etc.;hydrocarbon-based solvent such as benzene, toluene, xylene, ethylbenzene, hexane, octane, decane, etc.; ester-based solvent such as ethylacetate, butyl acetate, amyl acetate and the like. Among those,halogen-based hydrocarbon solvent, hydrocarbon-based solvent andether-based solvent are preferable. Further, the solvent may be usedalone, or in combination of two or more kind thereof. Additionally, theemployable solvent is not limited to the above examples. It ispreferable that the organic device of the present invention is formed byusing the material for luminescent coating formation.

EXAMPLES

This invention will be described in further detail with reference to theexamples, which do not limit the scope of this invention.

Example 1 Synthesis of Compound (A17)

The route for synthesis of Compound (A17) is shown as follows:

(1) Synthesis of Intermediate Product 1-1

2-pyridylzincbromide (13.5 g, 60.6 mmol), 1,3-diiodo benzene (20 g, 60.6mmol) and Pd(PPh₃)₄ (2.32 g, 2.0 mmol) were added in tetrahydrofurananhydride (300 milliliter) under the argon gas atmosphere, and theresultant solution was stirred for 8 hours at room temperature.

The resultant reaction solution added by water was extracted with methylacetate, and then the obtained was dried with the use of magnesiumsulfate anhydride, followed by vacuum concentration in an evaporator.The residue obtained was refined with silica gel column chromatography(dissolution solvent: methylene chloride) and as a result, the objectivecompound was obtained.

Produced Amount: 8.0 g, Yield: 47%

(2) Synthesis of Intermediate Product 1-2

Into a three neck flask, 3-bromobenzene-1-boronic acid (3.59 g, 17.9mmol), Intermediate Product 1-1 (6.04 g, 21.5 mmol) and Pd(PPh₃)₄ (0.62g, 0.54 mmol) were placed and the atmosphere in the flask was replacedwith argon gas. Dimethylformamide (50 milliliter) and an aqueoussolution (27 milliliter) of potassium carbonate (7.42 g, 53.7 mmol) wereadded to the resultant solution and then, it was refluxed under heatingfor 8 hours. The resultant reaction solution was extracted by toluene,followed by vacuum concentration. The obtained solid thereafter wasrefined with silica gel column chromatography (dissolution solvent:methylene chloride) and as a result, Intermediate Product 1-2 wasobtained.

Produced Amount: 4.78 g, Yield: 86%

(3) Synthesis of Intermediate Product 1-3

Into a 300 milliliter flask, of which atmosphere was already replacedwith argon gas, Intermediate Product 1-2 (4.0 g, 12.9 mmol) andtetrahydrofuran anhydride (100 milliliter) were placed and further,after cooling the resultant solution down to −60° C., a hexane solution(12.6 milliliter) of n-butyllithium 1.59 M was poured into the cooledsolution. The resultant reaction solution was stirred at the temperatureof −20° C. for 1 hour and then, the solution was cooled down to −60° C.,followed by adding tetrahydrofuran anhydride solution (40 milliliter) oftriisopropyl boride (6.28 g, 33.4 mmol) therein, then the resultantsolution was stirred for 1 hour. The temperature of the reactionsolution was elevated little by little up to the room temperature, andthe reaction solution was stood alone over a night. After adding 2Nhydrochloric acid (100 milliliter) to the resultant solution, stirringthe solution at room temperature for 1 hour, followed by separation ofan organic layer. The organic layer was dried with the use of magnesiumsulfate anhydride, followed by vacuum concentration in an evaporator andas a result, Intermediate Product 1-3 was obtained.

Produced Amount: 29.4 g, Yield: 83%

(4) Synthesis of Intermediate Product 1-4

Into a three neck flask, indan-2,9-fluorene-2′,7′-dibromide (7.63 g,17.9 mmol), Intermediate Product 1-13 (2.80 g, 17.9 mmol) and Pd(PPh₃)₄(0.62 g, 0.54 mmol) were placed and the atmosphere in the flask wasreplaced with argon gas. Dimethoxyethane (50 milliliter) and an aqueoussolution (27 milliliter) of sodium carbonate (5.69 g, 53.7 mmol) wereadded to the resultant solution and then, it was refluxed under heatingfor 8 hours. The resultant reaction solution was extracted by toluene,followed by vacuum concentration. The obtained solid thereafter wasrefined with silica gel column chromatography (dissolution solvent:methylene chloride) and as a result, Intermediate Product 1-4 wasobtained. Produced Amount: 5.37 g, Yield: 52%

(5) Synthesis of Intermediate Product 1-5

Into a three neck flask, 4-(N-carbazolyl)-phenylboronic acid (2.47 g,8.60 mmol), Intermediate Product 1-4 (3.82 g, 6.62 mmol) and Pd(PPh₃)₄(0.36 g, 0.3 mmol) were placed and the atmosphere in the flask wasreplaced with argon gas. Dimethoxyethane (50 milliliter) and an aqueoussolution (27 milliliter) of sodium carbonate (1.97 g, 18.6 mmol) wereadded to the resultant solution and then, it was refluxed under heatingfor 8 hours. The resultant reaction solution was extracted by toluene,followed by vacuum concentration. The obtained solid thereafter wasrefined with silica gel column chromatography (dissolution solvent:methylene chloride) and as a result, Intermediate Product 1-5 wasobtained.

Produced Amount: 3.13 g, Yield: 64%

(6) Synthesis of Compound (A17)

Into a flask, of which atmosphere was replaced with argon gas,Intermediate Product 1-5 (2.67 g, 3.62 mmol), iridium(III)acetylacetonate (Ir(acac)₃) (0.35 g, 0.72 mmol) and glycerol (50milliliter) were placed, and then it was refluxed under heating for 15hours. The precipitated solid was filtrated and washed by methanol. Theobtained solid thereafter was refined with silica gel columnchromatography (dissolution solvent: methylene chloride) and as aresult, Compound (A17) was obtained. It was confirmed in accordance with90 MHz ¹H-NMR and Field Desorption Mass Spectrometry (FD-MS) that theobtained was the objective compound. The result of the measurement inaccordance with FD-MS is shown as the following:

Produced Amount: 0.66 g, Yield: 38%, FD-MS: 2403 (M⁺, 100).

Example 2 Synthesis of Compound (A7)

The route for synthesis of Compound (A7) is shown as the following:

(1) Synthesis of Intermediate Product 2-1

Into a flask, of which atmosphere was replaced with argon gas,spiro[indan-2,9′-fluorene-2,7′-dibromide](5.62 g, 13.2 mmol), andtetrahydrofuran anhydride (50 milliliter) were placed and the resultantsolution was cooled down to −6° C., followed by pouring a hexanesolution (8.3 milliliter, 13.2 mmol) of n-butyllithium 1.59 M therein.The resultant reaction solution was stirred at the temperature of −20°C. for 1 hour and further, the solution was cooled down to −60° C., andthen, adding tetrahydrofuran anhydride solution (40 milliliter) oftriisopropyl boride (4.97 g, 26.4 mmol), the resultant solution wasstirred for 1 hour. The temperature of the reaction solution waselevated little by little up to the room temperature, and the reactionsolution was stood alone over a night. After adding 2N hydrochloric acid(100 milliliter) to the resultant solution, stirring the solution atroom temperature for 1 hour, followed by separation of an organic layer.The organic layer was dried with the use of magnesium sulfate anhydride,followed by vacuum concentration in an evaporator. The obtained solidthereafter was refined with silica gel column chromatography(dissolution solvent: methylene chloride) and as a result, IntermediateCompound 2-1 was obtained.

Produced Amount: 2.01 g, Yield: 39%

(2) Synthesis of Intermediate Product 2-2

Into a three neck flask, Intermediate Product 1-1 (1.41 g, 5.0 mmol),Intermediate Product 2-1 (1.96 g, 5.0 mmol) and Pd(PPh₃)₄ (0.35 g, 0.3mmol) were placed and the atmosphere in the flask was replaced withargon gas. Dimethoxyethane (20 milliliter) and an aqueous solution (7.5milliliter) of sodium carbonate (1.59 g, 15 mmol) were added to theresultant solution and then, it was refluxed under heating for 8 hours.The resultant reaction solution was extracted by toluene, followed byvacuum concentration. The obtained solid thereafter was refined withsilica gel column chromatography (dissolution solvent: methylenechloride) and as a result, Intermediate Product 2-2 was obtained.Produced Amount: 1.88 g, Yield: 75%

(3) Synthesis of Intermediate Product 2-3

Into a three neck flask, Intermediate Product 2-2 (1.65 g, 3.3 mmol),3,5-dichlorophenyl boronic acid (0.63 g, 3.3 mmol) and Pd(PPh₃)₄ (0.20g, 0.17 mmol) were placed and the atmosphere in the flask was replacedwith argon gas. Dimethylformamide (10 milliliter) and an aqueoussolution (5 milliliter) of potassium carbonate (1.38 g, 10.0 mmol) wereadded to the resultant solution and then, it was refluxed under heatingfor 8 hours. The resultant reaction solution was extracted by toluene,followed by vacuum concentration. The obtained solid thereafter wasrefined with silica gel column chromatography (dissolution solvent:methylene chloride) and as a result, Intermediate Product 2-3 wasobtained.

Produced Amount: 1.51 g, Yield: 81%

(4) Synthesis of Intermediate Product 2-4

In a three neck flask, Intermediate Product 2-4 (1.50 g, 2.65 mmol),4-(N-carbazolyl)-phenylboronic acid (1.90 g, 6.62 mmol), Pd₂(dba)₃ (0.12g, 0.13 mmol) and cesium carbonate (5.18 g, 15.9 mmol) were placed andthe atmosphere in the flask was replaced with argon gas.Tricyclohexylphosphin (0.10 g, 0.36 mmol) and dimethylformamide (20milliliter) and dimethlformamide (20 milliliter) were added to theresultant solution and then, it was refluxed under heating for 8 hours.The resultant reaction solution was extracted by toluene, followed byvacuum concentration. The obtained solid thereafter was refined withsilica gel column chromatography (dissolution solvent: methylenechloride) and as a result, Intermediate Product 2-4 was obtained.

Produced Amount: 1.61 g, Yield: 82%

(5) Synthesis of Compound (A7)

Into a flask, of which atmosphere was replaced with argon gas, theintermediate 2-4 (1.47 g, 1.5 mmol), Ir(acac)₃ (0.15 g, 0.3 mmol) andglycerol (30 milliliter) were placed, and then it was refluxed underheating for 15 hours. The precipitated solid was filtrated and washed bymethanol. The obtained solid thereafter was refined with silica gelcolumn chromatography (dissolution solvent: methylene chloride) and as aresult, Compound (A7) was obtained. It was confirmed in accordance with90 MHz ¹H-NMR and Field Desorption Mass Spectrometry (FD-MS) that theobtained was the objective compound. The result of the measurement inaccordance with FD-MS is shown as the following: Produced Amount: 0.23g, Yield: 25%, FD-MS: 3126 (M⁺, 100).

Example 3 Synthesis of Compound (A45)

The route for synthesis of Compound (A45) is shown as the following:

(1) Synthesis of Intermediate Product 3-1

Under the argon gas atmosphere,spiro[indan-2,9′-fluorene-2,7′-dibromide](5.63 g, 13.2 mmol), pinacolatediborane (8.04 g, 31.7 mmol), PdCl₂(dppf) (0.65 g, 0.79 mmol), potassiumacetate (7.73 g, 79.2 mmol), and dimethylsulfoxide (50 milliliter) wereplaced and then the resultant solution was stirred at 80° C. for 8hours. After water was added in the resultant reaction solution, theprecipitated solid was filtrated, and then dried. The obtained solidthereafter was refined with silica gel column chromatography(dissolution solvent: methylene chloride) and as a result, the objectivecompound was obtained. Produced Amount: 4.18 g, Yield: 81%

(2) Synthesis of Intermediate Product 3-2

Into a three neck flask, Intermediate Product 1-2 (5 g, 17.8 mmol),3,5-dibromophenyl boronic acid (4.98 g, 17.8 mmol) and Pd(PPh₃)₄ (1.0 g,0.9 mmol) were placed and the atmosphere in the flask was replaced withargon gas. Dimethoxyethene (50 milliliter) and an aqueous solution (27milliliter) of sodium carbonate (5.66 g, 53.4 mmol) were added to theresultant solution and then, it was refluxed under heating for 8 hours.The resultant reaction solution was extracted by toluene, followed byvacuum concentration. The obtained solid thereafter was refined withsilica gel column chromatography (dissolution solvent: methylenechloride).

Produced Amount: 6.37 g, Yield: 92%

(3) Synthesis of Intermediate Product 3-3

Into a three neck flask, Intermediate Product 3-2 (1.65 g, 4.23 mmol),Intermediate Product 3-1 (5.0 g, 10.6 mmol), tris(dibenzylideneaceton)dipalladium (0) (Pd(PPh₃)₄) (0.23 g, 0.2 mmol were placed and theatmosphere in the flask was replaced with argon gas. Dimethylformamide(50 milliliter) and an aqueous solution (13 milliliter) of potassiumcarbonate (2.49 g, 25.4 mmol) were added to the resultant solution andthen, it was refluxed under heating for 8 hours. The resultant reactionsolution was extracted by toluene, followed by vacuum concentration. Theobtained solid thereafter was refined with silica gel columnchromatography (dissolution solvent: methylene chloride), and as aresult, Intermediate Product 3-3 was obtained.

Produced Amount: 2.12 g, Yield: 75%

(4) Synthesis of Compound (A45)

Into a flask, of which atmosphere was replaced with argon gas,Intermediate Product 3-3 (2.0 g, 2.99 mmol), Ir(acac)₃ (0.29 g, 0.59mmol), and glycerol (50 milliliter) were placed and then the resultantsolution was refluxed under heating for 15 hours. The precipitated solidwas filtrated and washed by methanol. The obtained solid thereafter wasrefined with silica gel column chromatography (dissolution solvent:methylene chloride) and as a result, Compound (A45) was obtained. It wasconfirmed in accordance with 90 MHz ¹H-NMR and Field Desorption MassSpectrometry (FD-MS) that the Compound (A45) obtained was the objectivecompound. The result of the measurement in accordance with FD-MS isshown as the follows:

Produced Amount: 0.56 g, Yield: 43%, FD-MS:2478 (M⁺, 100).

Example 4 Fabrication of an Organic EL Device

A glass substrate (manufactured by GEOMATEC Company) of 25 mm×75 mm×1.1mm thickness having an ITO transparent electrode was cleaned byapplication of ultrasonic wave in isopropyl alcohol for 5 minutes andthen by exposure to ozone generated by ultraviolet light for 30 minutes.On the substrate, by using a solution prepared by dissolving Compound(A17) synthesized in Example 1 in chloroform, a film for the use of thelight emitting layer was formed in accordance with a spin coat process.The film thickness was 50 nm. On the film formed above, a film of1,3,5-tris(2-N-phenylbenzimidazololyl)benzene having a thickness of 50nm was formed. Thereafter, LiF as a reductive dopant was vapor depositedthereon and a LiF film was formed as the electron injecting layer (orthe cathode). On the LiF film, metallic aluminum was vapor deposited toform a metal cathode and an organic EL device was prepared.

Voltage, current density, current efficiency and power efficiency of thefabricated organic EL device were measured by conducting a test offeeding electric current, and further, a sate of light emission aboutthe light emitting surface after storing the device at the temperatureof 100° C. for 50 hours was observed. The results are shown in Table 1.

Example 5

An organic EL device was fabricated similarly as Example 4 except thatCompound (A7) synthesized in Example 2 was used in place of Compound(A17).

Voltage, current density, current efficiency and power efficiency of thefabricated EL device were measured by conducting a test of feedingelectric current, and further, a sate of light emission about the lightemitting surface after storing the device at the temperature of 100° C.for 50 hours was observed. The results are shown in Table 1.

Example 6

An organic EL device was fabricated similarly as Example 4 except that amixture obtained by adding 12% by mass of Compound (A45) synthesized inExample 3 into the following compound (CBP) was used in place ofCompound (A17).

Voltage, current density, current efficiency and power efficiency of thefabricated EL device were measured by conducting a test of feedingelectric current, and further, a sate of light emission about the lightemitting surface after storing the device at the temperature of 100° C.for 50 hours was observed. The results are shown in Table 1.

Comparative Example 1

An organic EL device was fabricated similarly as Example 4 except that amixture obtained by adding 12% by mass of the following compoundIr(ppy)₃ into the above compound (CBP) was used as a light emittinglayer in place of Compound (A17).

Voltage, current density, current efficiency and power efficiency of thefabricated EL device were measured by conducting a test of feedingelectric current, and further, a sate of light emission about the lightemitting surface after storing the device at the temperature of 100° C.for 50 hours was observed. The results are shown in Table 1.

Comparative Example 2

An organic EL device was fabricated similarly as Example 4 except that amixture obtained by adding 12% by mass of the following compound (H1)into aforementioned compound (CBP) was used in place of Compound (A17).

Voltage, current density, current efficiency and power efficiency of thefabricated EL device were measured by conducting a test of feedingelectric current, and further, a sate of light emission about the lightemitting surface after storing the device at the temperature of 100° C.for 50 hours was observed. The results are shown in Table 1. TABLE 1(H1)

Surface state of light emitting face after storing Ap- at the tem-Material plied Current Power perature in Volt- Current Effi- Effi- of100° C. Emitting age Density ciency ciency for Layer (V) (mA/cm²) (cd/A)(lumen/W) 50 hours Exam- (A17) 4.9 0.24 51.7 33.1 Emitting ple 4uniformly Exam- (A7) 5.1 0.26 44.2 27.2 Emitting ple 5 uniformly Exam-(A45)/ 5.8 0.26 41.9 22.7 Emitting ple 6 CBP uniformly Com- Ir(Ppy)₃/6   0.28 12.2  6.4 Emitting parative CBP non- Exam- uniformly ple 1 Com-(H1)/CBP) 6   0.28 26.2 13.7 Emitting parative non- Exam- uniformly ple2

As shown in Table 1, the organic EL devices of Examples 4 to 6 employedthe coordination metal complexes of the present invention are activatedeven under a low driving voltage, and also exhibits an excellentluminance and excellent power efficiency in comparison with the organicEl devices of Comparative Examples 1 and 2.

In addition, the organic EL devices of Examples 4 to 6 emit uniformlight for a long time due to their resistance to elevated temperature.On the other hand, as shown in Comparative Example 2, the devicesemployed the compounds having no spiro bond exhibit lower efficiency oflight emission due to the association between the molecules.

Example 7

(I) Synthesis of Complex 1

Complex (1) was synthesized as follows;(1) Synthesis of Compound 1

Under the atmosphere of argon gas, 2,7-dibromofluorene (5 g, 15.4 mmol),diphenylamine (10.4 g, 61.4 mmol), tris(dibenzilidenaceton)dipalladium(0) (0.71 g, 0.8 mmol) and sodium t-butoxide (4.84 g, 43.2 mmol) weresuspended into toluene anhydride (50 milliliter), and then a toluenesolution of 66% by mass containing tri-t-buthylphosphine (0.38milliliter, 1.3 mmol) was added in the resultant suspension, followed byrefluxing it under heating for 10 hours. The resultant reaction mixturewas filtrated with silica gel, and the obtained was washed by toluene.Oil obtained by distilling the solvent from the filtrated solution wasrefined with silica gel column chromatography (dissolution solvent:methylene chloride) and as a result, Compound 1 was obtained.

Product Amount: 5.86 g, Yield: 76%

(2) Synthesis of Compound 3

Lithium aluminum hydride (2.7 g, 70.5 mmol) was suspended intetrahydrofuran anhydride (100 milliliter), and then a tetrahydrofurananhydride solution (100 milliliter) of Compound 2 (8 g, 35.3 mmol) wasdropped in the suspension at room temperature. After 2 hours stirring,ethylacetate (100 milliliter) and water (100 milliliter) were poured inthe resultant reaction solution in this order. Subsequently, theresultant reaction solution was filtrated, and then an organic layer wasseparated by adding ethylacetate, followed by drying thereof with theuse of magnesium sulfate anhydride. The solvent of the organic layer wasdistilled, and as a result, Compound 3 was obtained.

Product Amount: 5.2 g, Yield: 63%

(3) Synthesis of Compound 4

After dissolving Compound 3 (5.2 g, 23.9 mmol) in methylene chloride (50milliliter), followed by adding N-bromosuccinimide (12.8 g, 71.7 mmol)at room temperature, and then the resultant solution was stirred for 6hours. Water (200 milliliter) was poured in the resultant reactionsolution, and the deposited solid was washed by ethanol, and as aresult, Compound 4 was obtained.

Product Amount: 6.9 g, Yield: 84%

(4) Synthesis of Compound 5

Under the atmosphere of argon gas, Compound 1 (5 g, 10 mmol), Compound 4(3.4 g, 10 mmol), toluene (15 millliter), dimethylsulfoxide (15milliliter), benzyltriethylammonium chloride (0.05 g, 0.22 mmol) and anaqueous solution (4 milliliter) of sodium hydroxide (50% by weight) weremixed and the resultant mixture was stirred at 80° C. for 8 hours. Afterpouring water (100 milliliter) and toluene (100 milliliter) in theresultant reaction solution, an organic layer was separated. The layerwas washed by saturated salt water, followed by drying thereof with theuse of magnesium sulfate anhydride. The solvent of the organic layer wasdistilled and then the residue obtained was refined with silica gelcolumn chromatography (hexane/methylene chloride) and as a result,Compound 5 was obtained. Product Amount: 3.9 g, Yield: 57%.(5) Synthesis of Compound 6

Under the atmosphere of argon gas, Compound 5 (3 g, 4.4mmol),2-pyridylzincbromide/0.5Mtetrahydrofuran (11.4 milliliter, 5.7mmol) and tetrakis(triphenylphosphino) palladium (0.15 g, 0.13 mmol)were poured in tetrahydrofuran anhydride, and then the resultant mixturewas refluxed under heating for 8 hours. The resultant reaction solutionadded by water was extracted with methyl acetate, and then the extractedsolution was dried with the use of magnesium sulfate anhydride, followedby vacuum concentration in an evaporator. The residue obtained wasrefined with silica gel column chromatography (dissolution solvent:methylene chloride), and as a result, Compound 6 was obtained.

Product Amount: 1.9 g, Yield: 63%.

(6) Synthesis of Complex 1

Into a flask, of which atmosphere was already replaced with argon gas,Compound (1.5 g, 2.2 mmol), Iridium(III) acetylacetnate (Ir(acac)₃)(1.08 g, 2.2 mmol) and glycerol (50 milliliter) were placed and theresultant was stirred at 250° C. for 15 hours, and then after pouring2-phenylpyridine (0.68 g, 4.4 mmol) in the reaction solution, theresultant solution was stirred at 250° C. for 10 hours. The precipitatedsolid was filtrated and washed by methanol. The obtained solid wasrefined with silica gel column chromatography (dissolution solvent:methylene chloride) and as a result, Complex 1 was obtained.

It was confirmed in accordance with 90 MHz ¹H-NMR and Field DesorptionMass Spectrometry (FD-MS) that the obtained was Complex 1 represented bythe above formula.

(II) Fabrication of an Organic EL Device

A glass substrate (manufactured by GEOMATEC Company) of 25 mm×75 mm×1.1mm thickness having an ITO transparent electrode was cleaned byapplication of ultrasonic wave in isopropyl alcohol for 5 minutes andthen by exposure to ozone generated by ultraviolet light for 30 minutes.On the substrate, a film of polyethylenedioxythiophene polystylenesulfonate (PEDOT/PSS) was formed in accordance with a spin coat process.The film thickness was 50 nm. Subsequently, a film was formed by using achloroform solution of the aforementioned conventional compound (CBP)mixed with Complex 1 of 12% by mass.

The film thickness was 50 nm. On the film formed above, a film of1,3,5-tris [2-N-phenylbenzimidazololyl?] benzene having a thickness of50 nm was formed. Thereafter, LiF as a reductive dopant was vapordeposited and a LiF film was formed as the electron injecting layer (orthe cathode). On the LiF film, metallic aluminum was vapor deposited toform a metal cathode and an organic EL device was prepared. Currentefficiency of the fabricated organic EL device was measured at thecondition of applying DC voltage as described in Table 1. The resultsare shown in Table 1.

Example 8

An organic EL device was fabricated similarly as Example 7 except thatComplex 2 was used in place of Complex 2 and then the same measurementas that of Example 7 was carried out. The results are shown in Table 1.In Example 8, Complex 2 was synthesized as follows.(1) Synthesis of Compound 7

Under the atmosphere of argon gas, 2,7-dibromofluorene (5 g, 15.4 mmol),4-(N-carbazolyl)-phenylboronic acid (11.1 g, 38.6 mmol),tetrakis(triphenylphosphino)palladium (1.07 g, 0.92 mmol), toluene (100milliliter) and an aqueous solution (46 milliliter) of 2M sodiumcarbonate were mixed and then the resultant mixture was refluxed underheating for 10 hours. The precipitated solid after pouring water in theresultant reaction solution was filtrated and washed by water. Theobtained solid was refined with silica gel column chromatography(dissolution solvent: methylene chloride) and as a result, Compound 7was obtained.(2) Synthesis of Compound 8

Compound 8 was obtained similarly as Synthesis of Compound 5 except thatCompound 7 (6.5 g, 10 mmol) was used in place of Compound 1. ProductAmount: 4.1 g, Yield: 50%(3) Synthesis of Compound 9

Compound 9 was obtained similarly as Synthesis of Compound 6 except thatCompound 8 (3.7 g, 4.4 mmol) was used in place of Compound 5. ProductAmount: 2.5 g, Yield: 68%(4) Synthesis of Complex 2

Complex 2 (complex-2) was obtained similarly as Synthesis of Complex 1except that Compound 9 (1.8 g, 2.2 mmol) was used in place of Compound6. Product Amount: 2.5 g, Yield: 68%

It was confirmed in accordance with 90 MHz ¹H-NMR and Field DesorptionMass Spectrometry (FD-MS) that the obtained was Complex 2 represented bythe above formula.

Comparative Example 3

An organic EL device was fabricated similarly as Example 7 except that amixture obtained by adding 12% by mass of Ir(ppy)₃ into CBP was used asa light emitting layer in place of Complex 1. The results were shown inTable 2. TABLE 2 Comparative Example 7 Example 8 Example 3 Material incomplex-1/CBP complex-2/CBP Ir(ppy)₃/CBP Emitting layer Applied 5.8 5.66.0 Voltage(V) Current 31.3 34.0 12.2 Efficiency (cd/A)

As shown in Table 2, they verify that the organic EL device of Examples7 and 8 which employ Complex 1 or Complex 2 of the present inventionexhibit an excellent luminance under a low driving voltage in comparisonwith the organic EL device of Comparative Example 3 employing aconventional material of Ir (ppy)₃.

Example 9

(I) Synthesis of Complex 3

(1) Synthesis of Compound 10

Under the atmosphere of argon gas, Compound 2 (5 g, 22 mmol),bis(pinacorate diborane (5.1 g, 20 mmol), [1,1-bis(diphenylphosphine)ferrocene] dichloropalladium (II)/metylene chloride complex (0.49 g, 0.6mmol) and potassium acetate (5.9 g, 60 mmol) were dissolved indimethylsulfoxide and then the resultant mixture was heated at 80° C.for 10 hours. The solid was precipitated by pouring water (100milliliter) in the resultant reaction solution and dried under vacuum.The obtained solid was refined with silica gel column chromatography(dissolution solvent: methylene chloride) and as a result, Compound 10was obtained. Product Amount: 5.0 g, Yield: 92%(2) Synthesis of Compound 11

Under the atmosphere of argon gas, Compound 10 (5.0 g, 18.4 mmol)2-bromopyridine (3.49 g, 22 mmol), tetrakis(triphenylphosphino)palladium (0.63 g, 0.55 mmol) and an aqueous solution (28 milliliter) of2M sodium carbonate were added in toluene (50 milliliter) and then theresultant was heated at 80° C. for 10 hours. The solid was precipitatedby pouring water (100 milliliter) in the resultant reaction solution anddried under vacuum. The obtained solid was refined with silica gelcolumn chromatography (dissolution solvent: methylene chloride) and as aresult, Compound 11 was obtained.

Product Amount: 3.4 g, Yield: 83%

(3) Synthesis of Compound 12

Under the atmosphere of argon gas, lithium aluminium hydride (1.2 g,30.5 mmol) was suspended in tetrahydrofuran anhydride (100 milliliter),and then Compound 11 (3.5 g, 3 mmol) was dropped in a tetrahydrofrananhydride solution (100 milliliter) at room temperature. After 2 hoursstirring thereof, ethylacetate (100 milliliter) and water were poured inthe resultant reaction solution in this order.

Subsequently, the resultant reaction solution was filtrated, and then anorganic layer was separated by adding ethylacetate, followed by dryingthereof with the use of magnesium sulfate anhydride. The solvent of theorganic layer was distilled, and as a result, Compound 12 was obtained.

Product Amount: 3.1 g, Yield: 95%).

(4) Synthesis of Compound 13

Into a solution of methylene chloride (50 milliliter) dissolved withCompound 12 (3.1 g, 14.5 mmol), N-bromosuccinimide (5.2 g, 29 mmol) wasadded, and then resultant was stirred at room temperature for 6 hours.The precipitated solid by adding water (200 milliliter) in the resultantreaction solution was washed by ethanol, and as result, Compound 13 wasobtained.

Product Amount: 4.5 g, Yield: 91%.

(5) Synthesis of Compound 14

Under the atmosphere of argon gas, 2-bromofluorene (2.45 g, 10 mmol),Compound 13 (3.4 g, 10 mmol), toluene (15 milliliter), dimethylsulfoxide(15 milliliter), benzyltriethylammonium chloride (0.05 g, 0.22 mmol) andan aqueous solution (4 milliliter) of sodium hydroxide (50% by weight)were mixed and the resultant mixture was stirred at 80° C. for 8 hours.After pouring water (100 milliliter) and toluene (100 milliliter) in theresultant reaction solution, an organic layer was separated. The layerwas washed by saturated salt water, followed by drying thereof with theuse of magnesium sulfate anhydride.

The solvent of the organic layer was distilled and then the residueobtained was refined with silica gel column chromatography(hexane/methylene chloride) and as a result, Compound 14 was obtained.

Product Amount: 2.3 g, Yield: 54%.

(6) Synthesis of Compound 15

Under the atmosphere of argon gas, Compound 14 (2.3 g, 5.4 mmol)4-vinylphnyl boronic acid (0.8 g, 5.4 mmol) andtetrakis(triphenylphosphino) palladium (0.19 g, 0.16 mmol) were added indimethoxyethane (10 milliliter) and an aqueous solution (8 milliliter)of 2M sodium carbonate and then the resultant was stirred at 60° C. for10 hours.

After pouring water (100 milliliter) and toluene (100 milliliter) in theresultant reaction solution, an organic layer was extracted, followed bydrying the organic layer with the use of magnesium sulfate anhydride.The solvent of the organic layer extracted was condensated under vacuumand then the residue obtained was refined with silica gel columnchromatography (hexane/methylene chloride) and as a result, Compound 15was obtained.

Product Amount: 1.1 g, Yield: 46%.

(7) Synthesis of Compound 16

N-vinylcarbazole (0.81 g, 4.2 mmol), Compound 15 (0.1 g, 0.22 mmol) and2,2-azobis(isobutylonitrile) (0.01 g, 0.061 mmol) were added inbutylacetate (10 milliliter), and then the resultant was stirred at 80°C. for 10 hours. The solid was precipitated by adding acetone in theresultant reaction solution and the solid was filtrated. Further, thesolid was dissolved in methylene chloride, and then the solid wasprecipitated by adding methanol therein, followed by washing the solidwith methanol, and as result, Compound 16 was obtained. Product Amount:0.83 g.

By means of NMR analysis, “M:n=5:95” in Compound 16 was proved. Inaddition, the molecular weight thereof was 18,000 as reduced topolystyrene.(7) Synthesis of Complex 3

Into a flask, of which atmosphere was already replaced by argon gas,Compound 6 (0.8 g), Ir (acac)₃ (0.1 g, 0.2 mmol) and glycerol (50milliliter) were poured, and then the resultant was stirred at 250° C.for 15 hours. Further, 2-phenylpyridine (0.068 g, 0.44 mmol) was addedin the resultant reaction solution, and then the resultant was stirredat 250° C. for 10 hours. The solid was precipitated by adding methanolin the resultant reaction solution and then the solid was filtrated,followed by washing the solid with methanol, and as result, Complex 3(complex-3) was obtained. Product Amount: 0.8 g

By means of elementary analysis of CHN and Ir, it was identified asComplex 3 represented by the aforementioned formula.

(II) Fabrication of an Organic EL Device

A glass substrate (manufactured by GEOMATEC Company) of 25 mm×75 mm×1.1mm thickness having an ITO transparent electrode was cleaned byapplication of ultrasonic wave in isopropyl alcohol for 5 minutes andthen by exposure to ozone generated by ultraviolet light for 30 minutes.On the substrate, a film of polyethylenedioxythiophene polystyrenesulfonate (PEDOT/PSS) was formed in accordance with a spin coatingprocess. The film thickness was 50 nm.

Subsequently, a film was formed by using a chloroform solution ofComplex 3. The film thickness was 50 nm. On the film formed above, afilm of 1,3,5-tris(2-N-phenylbenzimidazololyl)benzene having a thicknessof 50 nm was formed. Thereafter, LiF as a reductive dopant was vapordeposited and a LiF film was formed as the electron injecting layer (orthe cathode). On the LiF film, metallic aluminum was vapor deposited toform a metal cathode and an organic EL device was fabricated.

Current Efficiency of the fabricated organic EL device was measured atthe condition of applying DC voltage as described in Table 2 and furthera sate of light emission about the light emitting surface after storingthe device at the elevated temperature (110° C., after 50 hours) wasobserved. The results are shown in Table 3. TABLE 3 Comparative Example9 Example 4 Material in Emitting layer complex-3 complex-5 AppliedVoltage(V) 8.4 10.2 Current Efficiency (cd/A) 14.1 2.3 Surface state oflight emitting Good Found many face after storing at the dark spotstemperature of 100° C. for 50 hours

As shown in Table 3, it verifies that the organic EL device of Examples9 which employed Complex 3 as a material for the organic EL device ofthe present invention is activated under a low driving voltage andexhibits an excellent luminance and excellent resistance to elevatedtemperature in comparison with the organic EL device of ComparativeExample 4. In addition, as evidenced by Comparative Example 4, a metalcompound having an ester part is poor at thermal stability, therefore,many dark spots were generated in a device used such compound.

Example 10

An organic device was fabricated similarly as Example 9 except thatComplex 4 was used in place of Complex 3. Current efficiency of thefabricated organic EL device was measured at the condition of applyingDC voltage as described in Table 4 and further a sate of light emissionabout the light emitting surface after storing the device at theelevated temperature (110° C., after 50 hours) was observed. The resultsare shown in Table 4. In Example 10, Complex 4 was synthesized asfollows.(1) Synthesis of Compound 17

Under the atmosphere of argon gas, 2,7-dibromofluorene (3.24 g, 10mmol), Compound 13 (3.4 g, 10 mmol), toluene (15 milliliter),dimethylsulfoxide (15 milliliter), benzyltriethylammonium chloride (0.05g, 0.22 mmol) and an aqueous solution (4 milliliter) of sodium hydroxide(50% by weight) were mixed and the resultant mixture was stirred at 80°C. for 8 hours.

After pouring water (100 milliliter) and toluene (100 milliliter) in theresultant reaction solution, an organic layer was separated from it. Thelayer was washed by saturated salt water, followed by drying thereofwith the use of magnesium sulfate anhydride.

The solvent of the organic layer was distilled and then the residueobtained was refined with silica gel column chromatography(hexane/methylene chloride) and as a result, Compound 14 was obtained.

Product Amount: 2.2 g, Yield: 43%.(2) Synthesis of Copolymer 18

Under the atmosphere of argon gas, Compound 17 (0.15 g, 0.3 mmol) and2,5-dibromothiophene (1.38 g, 5.7 mmol) were added in dimethylformamide(10 milliliter) and then the polymerization of thereof carried out byusing bis(1,5-cyclooctadiene) nickel (0) as a catalyst in accordancewith a conventional method. The solid was precipitated by adding waterin the resultant reaction solution and the solid was washed withmethanol. The obtained solid was dried under vacuum, and as result,Compound 18 was obtained. Product Amount: 0.51 g

By means of NMR analysis, “M:n=5:95” in Compound 18 was proved. Inaddition, the molecular weight thereof was 18,000 as reduced topolystyrene.(3) Synthesis of Complex 4

Under the atmosphere of argon gas, Compound 18 (0.51 g) and Ir(acac)₃(0.13 g, 027 mmol) were added in metacresol, and then the resultant wasstirred at 250° C. for 12 hours. Subsequently, phenylpyridine (0.08 g,0.58 mmol) was added, in the resultant solution, followed by stirring at250° C. for 12 hours. After the reaction was over, reprecipitation wascarried out by adding acetone therein, and then the copolymer wasrecovered by filtration. A DMF solution of the copolymer was poured inacetone so as to cause reprecipitation, and then the precipitate wasfiltrated. The recovered precipitate was dried under vacuum and thenComplex 4 (complex-4) was obtained.

Product Amount: 0.52 g

By means of elementary analysis of CHN and Ir, it was identified asComplex 4 represented by the aforementioned formula.

Comparative Example 4

An organic device was fabricated similarly as Example 9 except thatComplex 5 was used in place of Complex 3, and the same measurement withExample 9 carried out on the organic device. The results are shown inTable 3. The molecular weight of Complex 5 was 17,000 as reduced topolystyrene, and it was proved as m:n=5:95 in the formula below.

Comparative Example 5

An organic device was fabricated similarly as Example 9 except thatComplex 6 (complex-6) was used in place of Complex 3, and the samemeasurement with Example 9 carried out on the organic device. Theresults are shown in Table 4. The molecular weight of Complex 5 was18,000 as reduced to polystyrene, and it was proved as m:n=5:95 in theformula below. TABLE 4 complex-6

Comparative Example 10 Example 5 Material in Emitting layer complex-4complex-6 Applied Voltage (V)  6.3  8.7 Current Efficiency (cd/A) 25.615.8

As shown in Table 4, it verifies that the organic EL device of Example10 which employs Complex 4 as a material for the organic EL device ofthe present invention is activated under a low driving voltage and alsoexhibits an enhanced current efficiency and excellent resistance toelevated temperature in comparison with the organic EL device ofComparative Example 5.

INDUSTRIAL APPLICABILITY

As explained above in details, since the coordination metal compound andthe material for an organic EL device of the present invention have atleast one ligand containing a spiro bond of large steric hindrance, theyare able to control association between the molecules, therefore theorganic EL device employing the compound or the material as an lightemitting layer exhibits an enhanced efficiency of light emission and hasgreat storage stability at elevated temperature. Further, since thecoordination metal compound and the material for an organic EL device ofthe present invention exhibits excellent solubility in an organicsolvent, and can be applied, as the material for luminescent coatingformation, to a wet film forming process such as a spin coating process,it is possible to provide an organic EL device at a lower cost.Therefore, the EL device employing the coordination metal compound andthe material for an organic EL device of the present invention isdistinctly useful as a practicable organic device.

1. A coordination metal compound comprising a metal cordinated with at least one ligand having a spiro bond.
 2. The coordination metal compound according to claim 1, wherein the coordination metal compound is represented by the general formula (1): (L₁)x-M-(P-M)y-(L₂)z  (1) wherein M represents a metal atom of iridium (Ir), platinum (Pt), osmium (Os), rhodium (Rh), rhenium (Re), palladium (Pd), ruthenium (Ru), tungsten (W), gold (Au) or silver (Ag); and Li represents a ligand cordinating to the metal atom M and also having a spiro bond, L₂ represents a ligand cordinating to the metal atom M, P represents a ligand interconnecting to the metal atom M when y is 1 or greater, x represents an integer of from 1 to the valence of a metal atom M, y represents an integer of from 0 to 4 and z represents an integer of from 0 to 4, further, plural M each represents the same with or different from each other when y is 1 or greater.
 3. The coordination metal compound according to claim 2, wherein Li represents a ligand represented by the general formula (2): A-(C)p-(B)q-(C)p-D-  (2) wherein A represents a group expressed by any of the general formulae (3) to (12):

wherein R each independently represents a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a carboxyl group, a halogen atom, a cyano group, a nitro group or a hydroxyl group; R may be bonded with each other to form a ring structure; V each independently represents a single bond, —CR₀R₀′—, —Si R₀R₀′—, —O—, —CO— or —NR₀ (R₀ and R₀′ each independently represents a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; E each independently represents a ring structure shown by a circle enclosing the symbol E, and a substituted or unsubstituted cycloalkane, of which a carbon atom may be substituted by a nitrogen atom, moiety having 3 to 6 ring carbon atoms, a substituted or unsubstituted aromatic hydrocarbon moiety having 4 to 6 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic moiety having 4 to 6 ring atoms; Q each independently represents an atomic group forming a ring structure, Z each independently represents —CR₀R₀′—, —SiR₀R₀′— or —GeR₀R₀′—; Ge means a germanium atom, while R₀ and R₀′ represent the same as aforementioned; a and b each independently represents an integer of from 0 to 4, and c, d, e and f each independently represents an integer of from 2 to 4; C each independently represents a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms and plural C, if any, may be the same with or different from each other; p represents an integer of form 0 to 20; B represents a group represented by the general formulae (13) to (15), and may be composed of each group singly or in combination thereof, and q represents an integer of from 0 to 20;

wherein R, V, E, Z, Q, a and b each independently represents the same as aforementioned; D represents a site coordinating to a metal atom; however, at least one of A or B in the general formula (2) comprises at least one of the structure having a spiro bond.
 4. The coordination metal compound according to claim 2, wherein, L¹ in the general formula (2) represents a ligand expressed by the general formula (16):

wherein A represents a group represented by any of the general formula (3) to (12); and plural A, if any, may be the same with or different from each other,

wherein R each independently represents a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 ring carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a carboxyl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group and the like; R may be bonded with each other to form a ring structure, V each independently represents a single bond, —CR₀R₀′—, —SiR₀R₀′—, —O—, —CO— or —NR₀ (R₀ and R₀′ each independently represents a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms), E each independently represents a ring structure shown by a circle enclosing the symbol E, and a substituted or unsubstituted cycloalkane, of which a carbon atom may be substituted by a nitrogen atom, moiety having 3 to 6 ring carbon atoms, a substituted or unsubstituted aromatic hydrocarbon moiety having 4 to 6 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic moiety having 4 to 6 ring atoms; Q each independently represents an atomic group forming a ring structure, Z each independently represents —CR₀R₀′—, —SiR₀R₀′—, or —GeR₀R₀′— wherein Ge means a germanium atom, while both R₀ and R₀′ represent the same as aforementioned; a and b each independently represents an integer of from 0 to 4, and c, d, e and f each independently represents an integer of from 2 to 4; C each independently represents a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms and plural C, if any, may be the same with or different from each other; s, t and u each independently represents an integer of from 0 to 20; B represents a group represented by any one of the general formulae (17) to (19), below and may be used alone or in combination thereof,

wherein R, V, Z, Q, a and b each independently represents the same as the aforementioned; D represents a site coordinating to a metal atom; however, at least one of A or B in the general formula (16) comprises at least one of the structure having a spiro bond.
 5. The coordination metal compound according to claim 3, wherein said D coordinating to a metal atom in the general formula (2) represents a group formed by removing a hydrogen atom from the molecule represented by the general formula (20):

wherein, Q₁ and Q₂ each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms or a derivative thereof, at least one of Q₁ and Q₂ represents a benzene ring or a derivative thereof, one of Q₁ and Q₂ forms a carbon atom-a metal atom bond with the aforementioned metal atom and the other one forms a coordination bond; Z₃ represents a single bond, —CR₀R₀′—, —SiR₀R₀—, —O—, —CO— or —NR₀, wherein, R₀ and R₀′ each independently represents the same as the aforementioned.
 6. The coordination metal compound according to claim 4, wherein the D coordinating to a metal atom represents a group formed by removing a hydrogen atom from the molecule represented by the general formula (20):

wherein Q₁ and Q₂ each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms or a derivative thereof, at least one of Q₁ and Q₂ represents a benzene ring or a derivative thereof, one of Q₁ and Q₂ forms a carbon atom-a metal atom bond with the aforementioned metal atom and the other one forms a coordination bond; Z₃ represents a single bond, —CR₀R₀′—, —SiR₀R₀′—, —O—, —CO— or —NR₀, wherein, R₀ and R₀′ each independently represents the same as the aforementioned.
 7. The coordination metal compound according to claim 3, wherein A in the general formula (2) represents a group selected from among the general formulae (5), (6) and (22) to (41), and also B in the general formula (2) represents a group selected from among the general formulae (42) to (44):

wherein, R, V, a, b, c, e and f each independently represents the same with the aforementioned, and also R₁ to R₁₀ each independently represents the same with aforementioned R; A₁ to A₄ each independently represents —CR′R″— —SiR′R″—, —O—, —NR′— and —CO—; wherein R′ and R″ each independently represents the same with aforementioned R, and also may be the same with or different from each other, further, at least two neighboring groups among A₁ to A₄ each independently are expresseed by —CR′R″—, and the neighboring R′s, the neighboring R″s or both R′ and R″ may bond saturatedly or unsaturatedly forming a ring structure having 4 to 50 carbon atoms as a result, w represents an integer of from 1 to
 10. 8. The coordination metal compound according to claim 4, wherein A in the general formula (16) represents a group selected from among the general formulae (22) to (41), and also B in the general formula (16) represents a group selected from the general formula (45) or (46):

wherein, wherein R, V, a, b, c, e and f each independently represents the same with the aforementioned, and also R₁ to R₁₀ each independently represents the same with aforementioned R, A₁ to A₄ each independently represents —CR′R″—, —SiR′R″—, —O—, —NR′— and —CO—; wherein R′ and R″ each independently represents the same with aforementioned R, and also may be the same with or different from each other, further, at least two neighboring groups among A₁ to A₄ each independently are expressed by —CR′R″—, and the neighboring R′s, the neighboring R″s or both R′ and R″ may bond saturatedly or unsaturatedly forming a ring structure having 4 to 50 carbon atoms as a result, w represents an integer of from 1 to
 10. 9. The coordination metal compound according to claim 2, wherein L₂ in the general formula (1) represents at least one kind selected from the group consisting of a halogen atom, an acetylaceton derivative, an 8-quinolinol derivative and a phenylpyridine derivative.
 10. The coordination metal compound according to claim 3, wherein said D in the general formula (2) represents a phenylpyridine group and said M in the general formula. (1) represents an iridium atom.
 11. The coordination metal compound according to claim 4, wherein said D in the general formula (16) represents a phenylpyridine group and said M in the general formula (1) represents an iridium atom.
 12. A material for an organic electroluminescence device comprising at least one compound having structure represented by the general formula (1′):

wherein X, Y¹ and Y² each independently represents a single bond, —CR′R″—, —Si R′R″—, —CO— or —NR′—; Q represents a carbon atom, a silicon atom or a germanium atom; Z represents a divalent group comprising a heavy metal complex; R′ and R″ each independently represents a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, R¹ to R⁸ each independently represents a hydrogen atom or a group selected from among a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 50 carbon atoms, a substituted or unsubstituted amino group having 1 to 50 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 50 carbon atoms, a substituted or unsubstituted dialkylamino group having 1 to 50 carbon atoms or a substituted or unsubstituted heterocyclic group having 1 to 50 carbon atoms, and an aryl group having 6 to 50 ring carbon atoms, an aryloxy group having 6 to 50 ring carbon atoms, an arylthio group having 6 to 50 ring carbon atoms, an arylamono group having 6 to 50 ring carbon atoms, a diarylamino group having 6 to 50 ring carbon atoms or an alkylarylamino group having 6 to 50 ring carbon atoms; and two neighboring substituent among R¹ to R⁸ may bond each other to form a ring structure.
 13. A material for an organic electroluminescence device comprising at least one compound having structure represented by the general formula (4′): (E¹)—(C¹)_(p1)—(C²)_(p2)-(Phos)-(C³)_(p3)—(C⁴)_(p4)-(E²)  (4′) wherein (Phos) represents a divalent group formed by removing two from among R¹ to R⁸, E¹ to E² each independently represents a hydrogen atom, or a group selected from among a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a carboxyl group, a halogen atom, a cyano group and a hydroxy group, C¹ to C⁴ each independently represents a group selected from a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms and a substituted or unsubstituted divalent aryl group having 6 to 50 carbon atoms; and p1 to p4 each independently represents an integer of from 0 to
 20. 14. A material for an organic electroluminescence device comprising a polymer obtained by polymerization or co-polymerization of a compound represented by the general formula (1′) according to claim 12, of which at least one of among R¹ to R⁸ represents a polymerizable group or an aromatic group having 6 to 50 ring carbon atoms with a polymerizable group.
 15. A material for an organic electroluminescence device comprising a polymer or a copolymer comprising a unit structure of a divalent group formed by removing two selected from among R¹ to R⁸ in the general formula (1′) according to claim
 12. 16. The material for an organic electroluminescence device according to claim 12, wherein Z in the general formula (1′) represents a divalent group formed by removing a hydrogen atom from the structure having a metal complex represented by the general formula (2′):

wherein M represents a metal atom selected from the group consisting of Pt, Os, Rh, Re, Pd, Ru, W Au and Ag; L¹ represents a metal coordination part represented by the general formula (3′):

which bonds to Y¹ and Y² in the general formula (1′); A¹ and A² in the general formula (3′) each independently represents a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms and a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, further at least one of two is a phenyl group or a substituted phenyl group, B¹ in the general formula (3′) represents a single bond, —CR′R″—, —SiR′R″—, —CO— or NR′— wherein R′ and R″ each independently represents a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; [L¹→M] in the general formula (2′) means that L¹ cordinates to a metal atom M and it is selected from the following:

wherein a carbon atom of L¹ bonds to a metal atom and a atom selected from the group consisting of N, O and S cordinates to the metal atom M; L² in the general formula (2′) represents a ligand cordinating to a metal atom and may be the same with or different from L¹, [M←L²] means that L² cordinates to a metal atom M and is selected from a σ bond of halogen atom or the following:

wherein an atom selected from a carbon atom of L², O and N bonds to a metal atom M; and an atom selected from the group consisting of N, O and S cordinates to a metal atom M; n in the general formula (2′) represents an integer of from 1 to x (x: valence of a metal atom) and m in the general formula (2′) represents an integer of from 0 to (x minus n).
 17. The material for an organic electroluminescence device according to claim 16, wherein, L² in the general formula (2′) represents at least one kind selected from the group consisting of a halogen atom, an acetylaceton derivative, an 8-quinolinol derivative and a phenylpyridine derivative:

wherein R¹¹ to R²⁷ each independently represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group, alkoxy group, alkylsilyl group or acryl group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
 18. The material for an organic electroluminescence device according to claim 16, wherein said M in the general formula (2′) represents an iridium (Ir) atom.
 19. An organic electroluminescence device comprising at least one of organic thin film layers and a light emitting layer sandwiched between a pair of electrodes consisting of an anode and a cathode, wherein a least one of the organic thin film layers comprises a coordination metal compound according to claim
 1. 20. The organic electroluminescence device according to claim 19, wherein the light emitting layer comprises a coordination metal compound according to claim
 1. 21. An organic electroluminescence device comprising at least one of organic thin film layers and a light emitting layer sandwiched between a pair of electrodes consisting of an anode and a cathode, wherein at least one of the organic thin film layers comprises the material of the coordination metal compound according to claim
 12. 22. The organic electroluminescence device according to claim 21 wherein the light emitting layer comprises the material for an organic electroluminescence device.
 23. A material for luminescent coating formation which comprises an organic solvent solution containing a coordination metal compound according to claim
 1. 24. A material for luminescent coating formation which comprises an organic solvent solution containing a coordination metal compound according to claim
 12. 25. An organic electroluminescence device comprising at least one of organic thin film layers including a light emitting layer sandwiched between a pair of electrodes consisting of an anode and a cathode, wherein at least one of the organic thin film layers is formed by using the material for luminescent coating formation according to claim
 23. 26. An organic electroluminescence device comprising at least one of organic thin film layers including a light emitting layer sandwiched between a pair of electrodes consisting of an anode and a cathode, wherein a least one of the organic thin film layers is formed by using the material for luminescent coating formation according to claim
 24. 